二氧化镍锂电池

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二氧化钴锂电池专利
检索词:LiCoO2 AND Battery: (147 patents)
PAT. NO.
Title
1 7,939,205 Thin-film batteries with polymer and LiPON electrolyte
layers and method
United States Patent
7,939,205
Klaassen
May 10, 2011
Abstract
A method and apparatus for making thin-film batteries having composite
multi-layered electrolytes with soft electrolyte between hard
electrolyte covering the negative and/or positive electrode, and the
resulting batteries. In some embodiments, foil-core cathode sheets each
having a cathode material (e.g., LiCoO.sub.2) covered by a hard
electrolyte on both sides, and foil-core anode sheets having an anode
material (e.g., lithium metal) covered by a hard electrolyte on both sides,
are laminated using a soft (e.g., polymer gel) electrolyte sandwiched
between alternating cathode and anode sheets. A hard glass-like
electrolyte layer obtains a smooth hard positive-electrode lithium-metal
layer upon charging, but when very thin, have randomly spaced
pinholes/defects. When the hard layers are formed on both the positive
and negative electrodes, one electrode's dendrite-short-causing defects
on are not aligned with the other electrode's defects. The soft
electrolyte layer both conducts ions across the gap between hard
electrolyte layers and fills pinholes.
Inventors: Klaassen; Jody J. (Minneapolis, MN)
Assignee: Cymbet Corporation (Elk River, MN)
Appl. No.: 12/850,078
Filed:
August 4, 2010
Related U.S. Patent Documents
Application Number Filing Date Patent Number Issue Date<TD< TD>
11458093
Jul., 2006
60699895
Jul., 2005
7776478
<TD< TD>
<TD< TD>
Current U.S. Class:
429/300 ; 429/304; 429/322
Current International Class:
Field of Search:
H01M 6/14
(20060101); H01M
6/18 (20060101)
429/47-347 427/1-601 29/623.1-625
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Primary Examiner: Yuan; Dah-Wei D
Assistant Examiner: Best; Zachary
Attorney, Agent or Firm: Kagan Binder, PLLC
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This invention is a divisional of U.S. Ser. No. 11/458,093, filed Jul.
17, 2006, now U.S. Pat. No. 7,776,478 by Klaassen, entitled "THIN-FILM
BATTERIES WITH POLYMER AND LIPON ELECTROLYTE LAYERS AND METHOD," which
claims benefit of U.S. Provisional Patent Application 60/699,895 filed
Jul. 15, 2005, which is hereby incorporated by reference in its entirety.
This is also related to U.S. patent application 10/895,445 entitled
"LITHIUM/AIR BATTERIES WITH LiPON AS SEPARATOR AND PROTECTIVE BARRIER AND
METHOD" filed Oct. 16, 2003 by J. Klaassen, the inventor of the present
application, and to U.S. patent application Ser. No. 11/031,217 entitled
"LAYERED BARRIER STRUCTURE HAVING ONE OR MORE DEFINABLE LAYERS AND METHOD"
filed Jan. 6, 2005, U.S. patent application Ser. No. 11/458,091, entitled
"THIN-FILM BATTERIES WITH SOFT AND HARD ELECTROLYTE LAYERS AND METHOD"and
U.S. patent application Ser. No. 11,458,097, entitled "APPARATUS AND
METHOD FOR MAKING THIN-FILM BATTERIES WITH SOFT AND HARD ELECTROLYTE
LAYERS"filed on Jul. 17, 2006, which are all incorporated herein in their
entirety by reference.
Claims
What is claimed is:
1. A method comprising: providing an anode component comprising a first
sheet that includes an anode material and a first LiPON layer covering
the anode material and having randomly spaced defects; providing a cathode
component comprising a second sheet that includes a cathode material that
includes lithium and a second LiPON layer covering the cathode material
and having randomly spaced defects; and sandwiching a polymer electrolyte
material between the LiPON layer covering the anode material of the first
sheet and the LiPON layer covering the cathode material of the second sheet,
wherein the polymer electrolyte material includes a gel and at least
partially fills and fixes the randomly spaced defects in the first and
second LiPON layers.
2. The method of claim 1, further comprising: providing a third sheet that
includes an anode material and a third LiPON layer covering the anode
material; providing a fourth sheet that includes a cathode material that
includes lithium and a fourth LiPON layer covering the cathode material;
sandwiching a polymer electrolyte material between the LiPON layer
covering the anode material of the third sheet and the LiPON layer covering
the cathode material of the fourth sheet; and sandwiching a polymer
electrolyte material between the LiPON layer covering the anode material
of the third sheet and the LiPON layer covering the cathode material of
the second sheet.
3. The method of claim 1, wherein the anode material of the first sheet
is deposited as a lithium-metal layer on a copper anode-current-collector
layer through the LiPON layer.
4. The method of claim 3, wherein the deposition of a lithium anode is
done by electroplating in a propylene carbonate/lithium-salt electrolyte
solution prior to assembling the cell.
5. The method of claim 1, wherein the first sheet includes a cathode
material on a face opposite the anode material and a LiPON layer covering
the cathode material, and the second sheet includes an anode material on
a face opposite the cathode material and a LiPON layer covering the anode
material; the method further comprising: providing a third sheet that
includes an anode material and a LiPON layer covering the anode material
on a first face, and a cathode material that includes lithium and a LiPON
layer covering the cathode material on a second face opposite the first
face; and sandwiching the polymer electrolyte material between the LiPON
layer covering the anode material of the third sheet and the UPON layer
covering the cathode material of the second sheet.
6. The method of claim 1, wherein the polymer electrolyte layer includes
a polyvinylidene difluoride, propylene carbonate, and a lithium salt.
7. The method of claim 1, further comprising the step of laminating two
or more battery cells together to form a laminated battery device.
8. The method of claim 1, wherein the laminated battery device comprises
a stack of two-sided anode current collectors and two-sided cathode
current collectors that are connected in parallel.
9. The method of claim 1, wherein the laminated battery device comprises
a stack of two-sided anode current collectors and two-sided cathode
current collectors that are connected in series.
10. The method of claim 1, wherein the polymer electrolyte layer is an
adhesive that provides a structural connection between the LiPon layers.
11. The method of claim 1, wherein the anode component comprises a current
collector onto which is deposited a cathode material.
12. The method of claim 1, wherein the anode component further comprises
a current collector, and wherein a layer of lithium is formed as an active
portion of the cathode component after assembly of the battery cell.
13. The method of claim 1, wherein the polymer electrolyte layer is sticky.
14. The method of claim 1, wherein the polymer electrolyte layer comprises
polyvinylidene difluoride, propylene carbonate, and a lithium salt.
15. The method of claim 1, wherein the polymer electrolyte layer comprises
MEEP.
16. The method of claim 1, wherein the negative electrode component
includes a negative-electrode current collector made of a metal that does
not readily alloy with lithium during a plating operation, and lithium
metal is plated onto the negative-electrode current collector through the
LiPON layer on the negative electrode component.
17. The method of claim 1, wherein the polymer electrolyte layer comprises
a polyphosphazene and a lithium salt.
Description
FIELD OF THE INVENTION
This invention relates to solid-state energy-storage devices, and more
specifically to a method and apparatus for making thin-film (e.g., lithium)
battery devices with a soft (e.g., polymer) electrolyte layer, and one
or more hard layers (e.g., LiPON) as electrolyte layer(s) and/or
protective barrier(s), and the resulting cell(s) and/or battery(s).
BACKGROUND OF THE INVENTION
Electronics have been incorporated into many portable devices such as
computers, mobile phones, tracking systems, scanners, and the like. One
drawback to portable devices is the need to include the power supply with
the device. Portable devices typically use batteries as power supplies.
Batteries must have sufficient capacity to power the device for at least
the length of time the device is in use. Sufficient battery capacity can
result in a power supply that is quite heavy and/or large compared to the
rest of the device. Accordingly, smaller and lighter batteries (i.e.,
power supplies) with sufficient energy storage are desired. Other energy
storage batteries (i.e., power supplies) with sufficient energy storage
are desired. Other energy storage devices, such as supercapacitors, and
energy conversion devices, such as photovoltaics and fuel cells, are
alternatives to batteries for use as power supplies in portable
electronics and non-portable electrical applications.
Another drawback of conventional batteries is the fact that some are
fabricated from potentially toxic materials that may leak and be subject
to governmental regulation. Accordingly, it is desired to provide an
electrical power source that is safe, solid-state and rechargeable over
many charge/discharge life cycles.
One type of an energy-storage device is a solid-state, thin-film battery.
Examples of thin-film batteries are described in U.S. Pat. Nos. 5,314,765;
5,338,625; 5,445,906; 5,512,147; 5,561,004; 5,567,210; 5,569,520;
5,597,660; 5,612,152; 5,654,084; and 5,705,293, each of which is herein
incorporated by reference. U.S. Pat. No. 5,338,625 describes a thin-film
battery, especially a thin-film microbattery, and a method for making same
having application as a backup or first integrated power source for
electronic devices. U.S. Pat. No. 5,445,906 describes a method and system
for manufacturing a thin-film battery structure formed with the method
that utilizes a plurality of deposition stations at which thin battery
component films are built up in sequence upon a web-like substrate as the
substrate is automatically moved through the stations.
U.S. Pat. No. 6,805,998 entitled "METHOD AND APPARATUS FOR INTEGRATED
BATTERY DEVICES" (which is incorporated herein by reference) issued Oct.
19, 2004, by Mark L. Jenson and Jody J. Klaassen (the inventor of the
present application), and is assigned to the assignee of the present
invention, described a high-speed low-temperature method for depositing
thin-film lithium batteries onto a polymer web moving through a series
of deposition stations.
K. M. Abraham and Z. Jiang, (as described in U.S. Pat. No. 5,510,209, which
is incorporated herein by reference) demonstrated a cell with a
non-aqueous polymer separator consisting of a film of polyacrylonitrile
swollen with a propylene carbonate/ethylene carbonate/LiPF.sub.6
electrolyte solution. This organic electrolyte membrane was sandwiched
between a lithium metal foil anode and a carbon composite cathode to form
the lithium-air cell. The utilization of the organic electrolyte allowed
good performance of the cell in an oxygen or dry air atmosphere.
As used herein, the anode of the battery is the positive electrode (which
is the anode during battery discharge) and the cathode of the battery is
the negative electrode (which is the cathode during battery discharge).
(During a charge operation, the positive electrode is the cathode and the
negative electrode is the anode, but the anode-cathode terminology herein
reflects the discharge portion of the cycle.)
U.S. Pat. No. 6,605,237 entitled "Polyphosphazenes as gel polymer
electrolytes" (which is incorporated herein by reference), issued to
Allcock, et al. on Aug. 12, 2003, and describes co-substituted linear
polyphosphazene polymers that could be useful in gel polymer electrolytes,
and which have an ion conductivity at room temperature of at least about
10.sup.-5 S/cm and comprising (i) a polyphosphazene having controlled
ratios of side chains that promote ionic conductivity and hydrophobic,
non-conductive side chains that promote mechanical stability, (ii) a
small molecule additive, such as propylene carbonate, that influences the
ionic conductivity and physical properties of the gel polymer
electrolytes, and (iii) a metal salt, such as lithium
trifluoromethanesulfonate, that influences the ionic conductivity of the
gel polymer electrolytes, and methods of preparing the polyphosphazene
polymers and the gel polymer electrolytes. Allcock et al. discuss a system
that has been studied extensively for solid-polymer electrolyte (SPE)
applications, which is one that is based on poly(organophosphazenes).
This class of polymers has yielded excellent candidates for use in SPEs
due to the inherent flexibility of the phosphorus-nitrogen backbone and
the ease of side group modification via macromolecular substitution-type
syntheses. The first poly(organophosphazene) to be used in a phosphazene
SPE (solid polymer electrolyte) was poly[bis(2-(2'-methoxyethoxy
ethoxy)phosphazene] (hereinafter, MEEP). This polymer was developed in
1983 by Shriver, Allcock and their coworkers (Blonsky, P. M., et al,
Journal of the American Chemical Society, 106, 6854 (1983)) and is
illustrated in U.S. Pat. No. 6,605,237.
Also, the following U.S. Pat. No. 7,052,805 (Polymer electrolyte having
acidic, basic and elastomeric subunits, published/issued on 2006 May 30);
U.S. Pat. No. 6,783,897 (Crosslinking agent and crosslinkable solid
polymer electrolyte using the same, 2004 Aug. 31); U.S. Pat. No. 6,727,024
(Polyalkylene oxide polymer composition for solid polymer electrolytes,
2004 Apr. 27); U.S. Pat. No. 6,392,008 (Polyphosphazene polymers, 2002
May 21); U.S. Pat. No. 6,369,159 (Antistatic plastic materials containing
epihalohydrin polymers, 2002 Apr. 9); U.S. Pat. No. 6,214,251 (Polymer
electrolyte composition, 2001 Apr. 10); U.S. Pat. No. 5,998,559
(Single-ion conducting solid polymer electrolytes, and conductive
compositions and batteries made therefrom; 1999 Dec. 7); U.S. Pat. No.
5,874,184 (Solid polymer electrolyte, battery and solid-state electric
double layer capacitor using the same as well as processes for the
manufacture thereof, 1999 Feb. 23); U.S. Pat. No. 5,698,664 (Synthesis
of polyphosphazenes with controlled molecular weight and polydispersity,
1997 Dec. 16); U.S. Pat. No. 5,665,490 (Solid polymer electrolyte, battery
and solid-state electric double layer capacitor using the same as well
as processes for the manufacture thereof, 1997 Sep. 9); U.S. Pat. No.
5,633,098 (Batteries containing single-ion conducting solid polymer
electrolytes, 1997 May 27); U.S. Pat. No. 5,597,661 (Solid polymer
electrolyte, battery and solid-state electric double layer capacitor
using the same as well as processes for the manufacture thereof, 1997 Jan.
28); U.S. Pat. No. 5,567,783 (Polyphosphazenes bearing crown ether and
related podand side groups as solid solvents for ionic conduction, 1996
Oct. 22); U.S. Pat. No. 5,562,909 (Phosphazene polyelectrolytes as
immunoadjuvants, 1996 Oct. 8); U.S. Pat. No. 5,548,060 (Sulfonation of
polyphosphazenes, 1996 Aug. 20); U.S. Pat. No. 5,414,025 (Method of
crosslinking of solid state battery electrolytes by ultraviolet radiation,
1995 May 9); U.S. Pat. No. 5,376,478 (Lithium secondary battery of
vanadium pentoxide and polyphosphazenes, 1994 Dec. 27); U.S. Pat. No.
5,219,679 (Solid electrolytes, 1993 Jun. 15); U.S. Pat. No. 5,110,694
(Secondary Li battery incorporating 12-Crown-4 ether, 1992 May 5); U.S.
Pat. No. 5,102,751 (Plasticizers useful for enhancing ionic conductivity
of solid polymer electrolytes, 1992 Apr. 7); U.S. Pat. No. 5,061,581
(Novel solid polymer electrolytes, 1991 Oct. 29); U.S. Pat. No. 4,656,246
(Polyetheroxy-substituted polyphosphazene purification, 1987 Apr. 7);
and U.S. Pat. No. 4,523,009, (Polyphosphazene compounds and method of
preparation, 1985 Jun. 11), which are all incorporated herein by reference.
Each discuss polyphosphazene polymers and/or other polymer electrolytes
and/or lithium salts and combinations thereof
U.S. patent application Ser. No. 10/895,445 entitled "LITHIUM/AIR
BATTERIES WITH LiPON AS SEPARATOR AND PROTECTIVE BARRIER AND METHOD" by
the inventor of the present application (which is incorporated herein by
reference) describes a method for making lithium batteries including
depositing UPON on a conductive substrate (e.g., a metal such as copper
or aluminum) by depositing a chromium adhesion layer on an electrically
insulating layer of silicon oxide by vacuum sputter deposition of 50 nm
of chromium followed by 500 nm of copper. In some embodiments, a thin film
of LiPON (Lithium Phosphorous OxyNitride) is then formed by low-pressure
(<10 mtorr) sputter deposition of lithium orthophosphate
(Li.sub.3PO.sub.4) in nitrogen. In some embodiments of the Li-air battery
cells, LiPON was deposited over the copper anode current-collector
contact to a thickness of 2.5 microns, and a layer of lithium metal was
formed onto the copper anode current-collector contact by electroplating
through the LiPON layer in a propylene carbonate/LiPF.sub.6 electrolyte
solution. In some embodiments, the air cathode was a
carbon-powder/polyfluoroacrylate-binder coating (Novec-1700) saturated
with a propylene carbonate/LiPF.sub.6 organic electrolyte solution. In
other embodiments, a cathode-current-collector contact layer having
carbon granules is deposited, such that atmospheric oxygen could operate
as the cathode reactant. This configuration requires providing air access
to substantially the entire cathode surface, limiting the ability to
densely stack layers for higher electrical capacity (i.e., amp-hours).
There is a need for rechargeable lithium-based batteries having improved
protection against dendrite formation and with improved density,
electrical capacity, rechargeability, and reliability, and smaller
volume and lowered cost.
BRIEF SUMMARY OF THE INVENTION
In some embodiments, the present invention includes a battery having an
electrolyte structure that combines a plurality of layers of different
electrolytes (e.g., hard-soft-hard). In some embodiments, a thin (0.1 to
1.0 micron) LiPON electrolyte layer serves as a hard coating on the
negative electrode preventing the formation of lithium dendrites
(especially when paired with a corresponding LiPON electrolyte layer
coating on the positive electrode) and/or providing an even (smooth), hard
layer of lithium metal on, or as part of, the negative electrode when the
battery is charged. In some embodiments, a thin (0.1 to 1.0 micron) LiPON
electrolyte on only one electrode (e.g., the negative electrode) may not
prevent the formation of lithium dendrites over the long term (e.g., many
thousands of discharge-recharge cycles), since the lithium growing
through a pinhole may only need to grow about 3 microns or less across
the electrolyte to short the battery (i.e., providing a metal electrical
conduction path directly from anode to cathode). When LiPON is also used
as a coating at the positive electrode (e.g., an electrode that includes
LiCoO.sub.2) the random locations of the pinholes will not line up (e.g.,
across the electrolyte from anode to cathode) so lithium would also need
to grow sideways in the electrolyte, which doubly ensures that lithium
plating at a defect site (which would typically form a dendrite) will not
short the battery. In some embodiments, a soft electrolyte layer bridges
the gap between the hard electrolyte layer on the negative electrode and
the hard electrolyte layer on the positive electrode. At both electrodes,
the LiPON layer also provides an improvement in environmental resistance
to water vapor and oxygen, especially during manufacture before the
battery is completed and otherwise sealed. In some embodiments, the soft
electrolyte includes a solid polymer electrolyte (SPE) layer that is
located between and contacts with the LiPON layer on the positive
electrode and the LiPON layer on the negative electrode. In some
embodiments, the electrolyte structure includes a polymer electrolyte
such as PEO-LiX (poly-ethylene oxide lithium-X, where LiX=a metal salt,
such as LiPF6, LiBF.sub.4, LiCF.sub.3SO.sub.4, CF.sub.3SO.sub.3Li
(lithium trifluoromethanesulfonate, also called triflate), lithium
bisperfluoroethanesulfonimide, lithium (Bis)
Trifluoromethanesulfonimide, and/or the like, for example). In some
embodiments, the electrolyte structure includes a polymer electrolyte
such as polyPN-LiX (Polyphosphazene with lithium-X, where
LiX.dbd.LiPF.sub.6, LiBF.sub.4, LiCF.sub.3SO.sub.4, and/or the like, for
example). In some embodiments, a small-molecule additive, such as
propylene carbonate, that influences the ionic conductivity and physical
properties of the polymer electrolytes is added to form a gel electrolyte
that better fills defects and acts as an adhesive.
The present invention provides both a method and an apparatus for making
thin-film batteries having composite (e.g., multi-layered) electrolytes
with a soft electrolyte layer between hard electrolyte layers covering
the negative and/or positive electrodes, and the resulting batteries. In
some embodiments, metal-core cathode sheets each having a cathode
material (e.g., LiCoO2) deposited on a metal foil, screen, or mesh (e.g.,
copper, nickel, or stainless steel) or a metal-covered insulator (e.g.,
a sputtered metal film on a polymer film, a SiO2-covered silicon wafer,
or an alumina or sapphire substrate) and is covered by a hard electrolyte
(some embodiments form such electrodes on both sides of the substrate),
and foil-core anode sheets having a anode material (e.g., lithium metal)
deposited on a metal foil (e.g., copper, nickel, or stainless steel) or
a metal-covered insulator (e.g., a sputtered metal film on a polymer film,
a SiO2-covered silicon wafer, or an alumina or sapphire substrate) and
is also covered by a hard electrolyte (some embodiments form such
electrodes on both sides of the substrate), and such sheets are laminated
using a soft (e.g., polymer gel) electrolyte sandwiched between
alternating cathode and anode sheets. In some embodiments, a hard
glass-like electrolyte layer obtains a smooth hard positive-electrode
lithium-metal layer upon charging, but when such a layer is made very thin,
will tend to have randomly spaced pinholes/defects. When the hard layers
are formed on both the positive and negative electrodes, one electrode's
dendrite-short-causing defects on are not aligned with the other
electrode's defects. The soft electrolyte layer conducts ions across the
gap between hard electrolyte layers and/or fills pinholes, thin spots,
and other defects in the hard electrolyte layers.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a schematic cross-section view of a lithium cell 100 of some
embodiments of the invention.
FIG. 1B is a schematic cross-section view of a lithium cell 101 of some
embodiments of the invention.
FIG. 1C is a schematic cross-section view of a lithium cell 102 of some
embodiments of the invention.
FIG. 2 is a schematic cross-section view of a lithium-battery
manufacturing process 200 of some embodiments of the invention.
FIG. 3 is a schematic cross-section view of a parallel-connected lithium
battery 300 of some embodiments of the invention.
FIG. 4 is a schematic cross-section view of a series-connected lithium
battery 400 of some embodiments of the invention.
FIG. 5A is a schematic cross-section view of a parallel-connected
screen-cathode current-collector contact lithium-battery 500 of some
embodiments of the invention.
FIG. 5B is a schematic cross-section view of a series-connected
screen-cathode-current-collector contact lithium-battery 501 of some
embodiments of the invention.
FIG. 6A is a perspective view of an electrode 600 having a
hard-electrolyte-covered current collector with a plating mask 119.
FIG. 6B is a perspective view of another electrode 601 having a
hard-electrolyte-covered current collector with a plating mask 119.
FIG. 6C is a perspective view of a plating system 610.
FIGS. 7A, 7B, 7C, 7D, 7E, and 7F are schematic cross-sectional views of
the fabrication of an atomic level matrix of copper and copper oxides as
cathodes on a substrate of some embodiments of the invention.
FIGS. 8A, 8B, 8C, 8D, and 8E are schematic cross-sectional views of the
fabrication of an atomic level matrix of copper and copper oxides as
cathodes on a copper foil substrate of some embodiments of the invention.
FIG. 9 is a schematic cross-section view of a parallel-connected
foil-cathode-current-collector contact lithium battery 900 of some
embodiments of the invention.
FIG. 10A is a schematic cross-section view of an encapsulated
surface-mount micro-battery 1000 of some embodiments of the invention.
FIG. 10B is a perspective view of an encapsulated surface-mount
micro-battery 1000 of some embodiments of the invention.
FIG. 11 is a flow chart of a method 1100 for making a battery cell according
to some embodiments of the invention.
FIG. 12 is a flow chart of a method 1200 for making a stacked battery
according to some embodiments of the invention.
FIG. 13 is an exploded perspective view of an embodiment of a device as
part of a system.
FIG. 14 is an exploded perspective view of another embodiment of a device
as part of a portable system.
DETAILED DESCRIPTION OF THE INVENTION
Although the following detailed description contains many specifics for
the purpose of illustration, a person of ordinary skill in the art will
appreciate that many variations and alterations to the following details
are within the scope of the invention. Accordingly, the following
preferred embodiments of the invention are set forth without any loss of
generality to, and without imposing limitations upon the claimed
invention.
In the following detailed description of the preferred embodiments,
reference is made to the accompanying drawings that form a part hereof,
and in which are shown by way of illustration specific embodiments in which
the invention may be practiced. It is understood that other embodiments
may be utilized and structural changes may be made without departing from
the scope of the present invention.
The leading digit(s) of reference numbers appearing in the Figures
generally correspond to the Figure number in which that component is first
introduced, such that the same reference number is used throughout to
refer to an identical component, which appears in multiple Figures.
Signals (such as, for example, fluid pressures, fluid flows, or electrical
signals that represent such pressures or flows), pipes, tubing or conduits
that carry the fluids, wires or other conductors that carry the electrical
signals, and connections may be referred to by the same reference number
or label, and the actual meaning will be clear from its use in the context
of the description.
Terminology
In this description, the term metal applies both to substantially pure
single metallic elements and to alloys or combinations of two or more
elements, at least one of which is a metallic element.
The term substrate or core generally refers to the physical structure that
is the basic work piece that is transformed by various process operations
into the desired microelectronic configuration. In some embodiments,
substrates include conducting material (such as copper, stainless steel,
aluminum and the like), insulating material (such as sapphire, ceramic,
or plastic/polymer insulators and the like), semiconducting materials
(such as silicon), non-semiconducting, or combinations of semiconducting
and non-semiconducting materials. In some other embodiments, substrates
include layered structures, such as a core sheet or piece of material (such
as iron-nickel alloy and the like) chosen for its coefficient of thermal
expansion (CTE) that more closely matches the CTE of an adjacent structure
such as a silicon processor chip. In some such embodiments, such a
substrate core is laminated to a sheet of material chosen for electrical
and/or thermal conductivity (such as a copper, aluminum alloy and the
like), which in turn is covered with a layer of plastic chosen for
electrical insulation, stability, and embossing characteristics. An
electrolyte is a material that conducts electricity by allowing movement
of ions (e.g., lithium ions having a positive charge) while being
non-conductive or highly resistive to electron conduction. An electrical
cell or battery is a device having an anode and a cathode that are separated
by an electrolyte. A dielectric is a material that is non-conducting to
electricity, such as, for example, plastic, ceramic, or glass. In some
embodiments, a material such as LiPON can act as an electrolyte when a
source and sink for lithium are adjacent the LiPON layer, and can also
act as a dielectric when placed between two metal layers such as copper
or aluminum, which do not form ions that can pass through the LiPON. In
some embodiments, devices include an insulating plastic/polymer layer (a
dielectric) having wiring traces that carry signals and electrical power
horizontally, and vias that carry signals and electrical power vertically
between layers of traces.
In some embodiments, an anode portion of a thin-film solid-state battery
is made (as described in U.S. patent application Ser. No. 10/895,445
discussed above) using a method that includes depositing LiPON on a
conductive substrate (e.g., a metal such as copper or aluminum) that is
formed by depositing a chromium adhesion layer on an electrically
insulating layer of silicon oxide (or on a polymer sheet) using
vacuum-sputter deposition of 50 nm of chromium followed by 500 nm of copper.
In some embodiments, a thin film of LiPON (Lithium Phosphorous OxyNitride)
is then formed by low-pressure (<10 mtorr) sputter deposition of lithium
orthophosphate (Li.sub.3PO.sub.4) in nitrogen, or by sputtering from a
LiPON source. In some embodiments LiPON is deposited over the copper anode
current-collector contact to a thickness of between 0.1 microns and 2.5
microns. In some embodiments, a layer of lithium metal is formed onto the
copper anode current-collector contact by electroplating through the
LiPON layer (which was earlier deposited on the copper anode
current-collector contact) in a propylene carbonate/LiPF.sub.6 organic
electrolyte solution. The LiPON acts as a protective layer during
fabrication of the battery, and in the assembled battery, it operates as
one layer of a multi-layer electrolyte. (In other embodiments, the layer
of lithium metal of the anode is formed by an initial charging operation
after the battery is assembled.) In some embodiments, a cathode portion
of the thin-film solid-state battery is made sputtering LiCoO.sub.2 onto
a first of metal foil from a LiCoO.sub.2 source, over which is deposited
a LiPON layer, which in the assembled battery, operates as another layer
of the multi-layer electrolyte. In some embodiments, a solid or gel
polymer electrolyte is used as a structural connection or adhesive between
the two LiPON electrolyte layers, as well as forming an ion-conductive
path between the positive and negative electrodes of the battery.
It is desirable, in some embodiments, to form a very thin electrolyte.
If a single very thin layer of LiPON is used, it tends to have defects
(e.g., thin spots or pinholes) and lithium ions will preferentially travel
through these paths of least resistance and plate to spike-shaped
lithium-metal dendrites that short out the battery. If a single very thin
solid or gel polymer electrolyte layer is used, any surface irregularities
(e.g., bumps or ridges in the anode or cathode material) will tend to
connect through the electrolyte and short the battery. By having two
independently formed very thin LiPON (hard) electrolyte component layers,
one formed on the battery's anode and another formed on the battery's
cathode, any such thin spots or pinholes in one layer will not line up
with a thin spot or pinhole in the other layer. The third electrolyte layer
(e.g., a soft polymer electrolyte that conducts lithium ions between the
two LiPON layers) made of a solid and/or gel polymer electrolyte material
does not get shorted out by bumps or other irregularities in either
electrode since those irregularities will tend to be coated with LiPON
and/or the corresponding spot on the other side will be coated with LiPON.
Accordingly, one or more (even all) of the plurality of layers can be made
very thin without the danger of having an initial short (from a polymer
electrolyte that is too thin allowing the anode and cathode to touch) or
a later-developed short (from a pinhole in a LiPON electrolyte layer that
allows formation of a lithium-metal dendrite after one or more
charge/discharge cycles). Further, the dense, hard, glass-like LiPON
layer causes the lithium ions that pass through it to form a lithium-metal
layer that is dense and smooth. In other embodiments, one or more other
hard and/or glass-like electrolyte layers are used instead of one or more
of the LiPON layers.
U.S. Pat. No. 6,605,237 entitled "Polyphosphazenes as gel polymer
electrolytes" discusses MEEP (poly[bis(2-(2'-methoxyethoxy
ethoxy)phosphazene]) and other polymers, which are used in some
embodiments of the present invention as structural connector and polymer
electrolyte sublayer between two UPON sublayers. The polyphosphazene
(herein called polyPN) used as the connective layer is soft and sticky.
Its adhesive properties are what allow the electrode to be and to remain
joined. Its softness allows for defect correction and/or for defects to
not cause poor battery performance and reliability. In other embodiments,
other soft or gel-like ion-conducting polymers are used.
U.S. Pat. Nos. 4,523,009, 5,510,209, 5,548,060, 5,562,909, 6,214,251,
6,392,008 6,605,237, and 6,783,897 (which are all incorporated herein by
reference) each discuss polyphosphazene polymers and/or other polymer
electrolytes and/or various lithium salts and compounds that can be used
as, or included in, one or more component layers of an electrolyte in some
embodiments of the present invention.
The term vertical is defined to mean substantially perpendicular to the
major surface of a substrate. Height or depth refers to a distance in a
direction perpendicular to the major surface of a substrate.
FIG. 1A is a schematic cross-section view of a lithium cell 100 of some
embodiments of the invention. In some embodiments, cell 100 includes a
first sheet 111 (a cathode or positive-electrode subassembly) having a
first metal foil 110 (which acts as a current collector) onto which is
deposited a film of cathode material 112, such as, for example,
LiCoO.sub.2, for example, by sputtering from a LiCoO.sub.2 target, and
over which is deposited a relatively hard LiPON layer 114 (which acts as
a hard-electrolyte current spreader). In some embodiments, cell 100
includes a second sheet 121 (an anode or negative-electrode subassembly)
having a second metal foil 120 (which acts as a current collector) onto
which is deposited a film of LiPON 124 (which acts as a hard-electrolyte
current spreader and as an environmental barrier for lithium that is later
plated through this layer), and a layer of lithium 122 (which forms the
active portion of the anode or negative-electrode) is plated through the
LiPON film 124 (either before or after the entire battery is assembled:
if the cathode contains sufficient lithium to start, then the anode
lithium layer is formed after assembly by the initial charging of the
battery, while if the cathode has little or no lithium to start with, then
the anode lithium layer is formed before assembly, e.g., by electroplating
in a liquid electrolyte or solution from an external sacrificial
lithium-metal electrode). In some embodiments, a sheet or layer of polymer
electrolyte 130 is sandwiched between the first sheet 111 and the second
sheet 121. In some embodiments, the layer of the polymer electrolyte is
deposited onto LiPON layer 114, LiPON layer 124, or a portion of the
polymer electrolyte is deposited onto both LiPON layer 114 and LiPON layer
124, and then the first sheet 111 and the second sheet 121 are pressed
together or otherwise assembled (in some embodiments, two or more of the
sheets are squeezed together between a pair of rollers).
In some embodiments, it is the hard-soft-hard combination of electrolyte
layers that provide a low-cost, high-quality, high-reliability, highly
rechargeable battery system. In some embodiments, the hard layers act as
protective barrier layers during manufacture and as current spreader
electrolytes that obtain a smooth hard layer of lithium on the anode upon
charging. In some embodiments, the hard layers are or include a glass or
glass-like electrolyte material (e.g., LiPON). When they are made very
thin (in order to increase cell conductivity and reduce cell resistance),
these hard layers tend to have randomly spaced pinholes, bumps, or other
defects (thicker layers can eliminate many such defects, but will have
decreased cell conductivity and increased cell resistance). When the hard
layers are formed on both the positive electrode and the corresponding
negative electrode, the pinholes and defects of the electrolyte covering
one electrode will tend not to be aligned with the pinholes and defects
of the electrolyte covering the other electrode. The soft electrolyte
layer both conducts ions across the gap between hard layers and tends to
fill the pinholes and defects of the hard electrolyte coverings. In some
embodiments, the soft electrolyte layer can be a solid or gel polymer
electrolyte (these also act as adhesives to hold the cells together and
as seals to reduce contamination of the cell from environmental factors
and to reduce leakage of the soft electrolyte layer), or can be a liquid
electrolyte, optionally infused in a structural element (such as a sponge,
screen, or ridges formed of a host solid-polymer (e.g., polyethylene,
polypropylene, fluoroethylene or the like) on one or more of the hard
electrolyte layers (e.g., by microembossing).
In some embodiments, the soft electrolyte layer includes a gel that
includes a polyvinylidene difluoride (PVdF), propylene carbonate, and a
lithium salt. PVdF is a polymer that does not conduct lithium ions, that
is, lithium salts will not dissolve in PVdF. However, PVdF can be swollen
with a liquid such as propylene carbonate in which a lithium salt has been
dissolved. The gel that results can be used as a soft electrolyte.
In some embodiments, the thickness of each of the hard electrolyte layers
is one micron or thinner, and the thickness of the soft electrolyte layer
is about three microns or thinner. The structure shown in FIG. 1A is also
represented in the following Table 1:
TABLE-US-00001 TABLE 1 Reference Function or Number Property Example
Materials . . . optionally, more battery layers stacked above . . . 110
cathode metal foil (e.g., one that does not alloy with current Li, such
as copper, nickel, stainless steel and collector the like), metal screen,
or metal film on polymer film or SiO.sub.2 layer on Si wafer, (can have
electrode formed on both sides for battery stack) 112 cathode LiCoO.sub.2
(sputtered or powder-pressed in place), material carbon powder, CuO
powder (any of the above can be infused with polyPN electrolyte material
to increase conductivity and lithium transport), or atomic matrix of
copper and copper oxides (which, in some embodiments, includes a tapered
composition Cu and O structure with more copper towards the top and more
oxygen towards the bottom, e.g., Cu metal gradually mixed
to . . .Cu.sub.4O. . .Cu.sub.2O. . .Cu.sup.+O.sup.--. . .CuO) 114 hard
LiPON or electrolyte other lithium-glass material 130 soft polyPN with
lithium (e.g., LiPF.sub.6), or other electrolyte polymer (e.g., PEO,
polypropylene, etc.) electrolyte material 124 hard LiPON or electrolyte
other lithium-glass material 122 anode Lithium, (can be plated through
the hard material (e.g., LiPON) layer before or after assembly) (could
be zinc with suitable changes to electrolytes and cathode material) 110
anode metal foil (e.g., copper), metal screen, or current metal film on
polymer film or SiO.sub.2 layer on Si collector wafer, (can have electrode
formed on both sides for battery stack) . . . optionally, more battery
layers stacked below
FIG. 1B is a schematic cross-section view of a lithium cell 101 of some
embodiments of the invention. In some embodiments, cell 101, which is
assembled in an uncharged state, includes a first sheet 111 (a cathode
or positive-electrode subassembly) similar to that of FIG. 1A, except that
the hard electrolyte 114 extends laterally over first metal foil 110 well
beyond the lateral edges of the film of cathode material 112. In some
embodiments, the lateral extent of cathode material 112 (such as, for
example, LiCoO.sub.2, for example) is defined using photoresist and
lithographic processes similar to those used for semiconductor integrated
circuits (e.g., the cathode material is masked using photoresist, or a
hard material such as SiO.sub.2 covered by photoresist and etched and the
photoresist is removed so that the hard layer (e.g., SiO.sub.2) acts as
the mask, to define the lateral extent of cathode material 112 (e.g.,
LiCoO.sub.2), and the mask is then removed. The hard electrolyte layer
114 (e.g., LiPON) is deposited on the cathode material 112 as well as onto
substrate 110 around the sides of cathode material 112. This sideward
extension of the hard UPON layer 114 acts as a seal to the sides of the
lithium in the cathode to protect it from environmental contaminants such
as oxygen or water vapor. In some embodiments, cell 101 includes a second
sheet 121 (an anode or negative-electrode subassembly similar to that of
FIG. 1A, except that no lithium is yet present) having a second metal foil
120 (which acts as a current collector) onto which is deposited a film
of LiPON 124 (which acts as a hard-electrolyte current spreader and as
an environmental barrier for lithium that is later plated through this
layer), and a mask layer 119 around all of the sides of what will be plated
lithium layer 122 (see FIG. 1C) that is later plated through the portions
of LiPON film 124 not covered by mask 119 (after the entire battery is
assembled). (In other embodiments, mask layer 119 is an electrical
insulator, such as SiO.sub.2, deposited directly on metal foil 120, and
photolithographically patterned to expose the metal substrate in the
center, and the hard electrolyte layer LiPON film 124 is deposited on top
of the mask layer). In some embodiments, the mask material 119 is
photoresist and/or an insulator such as SiO.sub.2 that have lateral
extents that are photolithographically defined. As above, in some
embodiments, a layer of soft polymer electrolyte 130 (either a solid
polymer electrolyte (SPE) or a gel or liquid polymer electrolyte) (such
as polyphosphazene having lithium salts such as LiPF.sub.6 to assist
lithium conductivity) is sandwiched between the first sheet 111 and the
second sheet 121.
FIG. 1C is a schematic cross-section view of a lithium cell 102 of some
embodiments of the invention. In some embodiments, the lithium metal layer
122 is plated before assembly (a combination of the methods described for
FIG. 6C and FIG. 2 below). In other embodiments, a battery 101 (such as
shown in FIG. 1B) is assembled before any lithium metal is in the anode
assembly 121, and is initially charged by plating lithium from the cathode
112 through electrolyte layers 114, 130, and 124 and onto the anode current
collector 120 to form lithium metal layer 122.
FIG. 2 is a schematic cross-section view of a lithium-battery
manufacturing process 200 of some embodiments of the invention. In some
embodiments, one or more double-sided anode sheets 121 are alternated with
one or more cathode sheets 111 (wherein an cathode material 112 is
deposited on both major faces of foil 110 inside of LiPON layer 114), with
a polymer layer 130 placed or formed between each sheet. In some
embodiments of anode sheets 121, an anode material 122 is deposited on
both major faces of foil 120 inside of (or plated through) LiPON layer
124 (note that, in some embodiments, by this stage, the mask 119 (see FIG.
1B) has been removed from the lateral sides of the anode after lithium
metal has been pre-electro-plated through the LiPON not covered by the
mask 119 onto current collector 121 using a liquid electrolyte and a
lithium sacrificial electrode.
In some embodiments, the soft polymer electrolyte layer 130 is spun on
as a liquid and then dried. In other embodiments, the soft polymer
electrolyte layer 130 is dip coated. In other embodiments, the soft
polymer electrolyte layer 130 is cast on. In some embodiments, the soft
polymer electrolyte layer 130 is deposited from a liquid source 225,
"squeegeed" (by squeegee 221) and/or doctor-bladed (by doctor-blade 222)
in place onto both sides of each foil-core double-sided anode sheet 121
(having previously had LiPON layer 124 and anode layer 122 formed thereon),
and onto both sides of each foil-core double-sided cathode sheet 111
(having previously had cathode-material layer 112 and LiPON layer 114
formed thereon). In some embodiments, the soft polymer electrolyte layer
130 is deposited by an apparatus that is essentially an offset printing
press, wherein a liquid soft polymer electrolyte material and/or solvent
mix ("ink") is printed to the areas to which the soft polymer electrolyte
layer 130 is desired.), and the stack is laminated together ("calendared"
e.g., by being pressed between rollers 250 (for example, pressed between
rubber-coated steel rollers, which, in some embodiments, are heated (e.g.,
by flowing hot oil inside the rollers)). Note that rollers 250 are
schematically shown relative to two central battery layers, where
In some embodiments, two or more such resulting stacks are then laminated
together in a similar fashion. In other embodiments, all of the
alternating layers of a battery device are laminated in a single pressing
step.
FIG. 3 is a schematic cross-section view of a parallel-connected lithium
battery 300 of some embodiments of the invention, resulting from the
laminating method of FIG. 2. In some embodiments, the outermost layer 111
and the outermost layer 121 are single sided, having a metal face facing
outwards. In other embodiments, all layers 111 are identical one to
another (and each is mirror-symmetrical about the center plane of foil
110), and all layers 121 are identical one to another (and each is
mirror-symmetrical about the center plane of foil 120). In some
embodiments, the edges of layers 111 are electrically connected to one
another (for example, soldered, spot-welded or pressed together on the
right-hand side) to form external cathode current-collector contact 321,
and the edges of layers 121 are electrically connected to one another (for
example, soldered, spot-welded or pressed together on the left-hand side)
to form external anode current-collector contact 322, thus connecting all
the cells in parallel to provide higher output current. In some
embodiments, 1- to 30-mA-hour (or more) single cells are thus formed
(depending on the area of each cell), and the battery has an amp-hour
capacity of about the sum of the parallel cells.
TABLE-US-00002 TABLE 2 Materials List for FIG. 3 - 1 repeat unit Material
Thickness Layer Mass (microns) (mg/cm.sup.2) 1/2 cathode collector foil*
1.5 and up (e.g., 6.25) 4.94 Nickel seed 0.1 to 0.3 (e.g., 0.3) 0.27
LiCoO.sub.2 0.5 to 10 (e.g., 5.0) 2.80 LiPON (cathode protect) 0.1 to 2.5
(e.g., 1.0) 0.21 soft polymer electrolyte and/or 0.5 to 10 (e.g., 5.0)
0.75 "glue" LiPON (anode protect) 0.1 to 2.5 (e.g., 1.0) 0.21 Lithium
(plated from LiCoO.sub.2) about 0.3 times the 0.08 LiCoO.sub.2 thickness
(e.g., 1.5) Copper (or Al, Ni, stainless steel, 0.1 to 1 (e.g., 0.25) 0.22
and the like) (used as the Li plate surface) Anode collector foil 3.0 and
up (e.g., 12.5) 9.88 Copper (or Al, Ni, stainless steel, 0.1 to 1 (e.g.,
0.25) 0.22 and the like) (used as the Li plate surface) Lithium (plated
from LiCoO.sub.2) about 0.3 times the 0.08 LiCoO.sub.2 thickness (e.g.,
1.5) LiPON (anode protect) 0.1 to 2.5 (e.g., 1.0) 0.21 soft polymer
electrolyte and/or 0.5 to 10 (e.g., 5.0) 0.75 "glue" LiPON (cathode
protect) 0.1 to 2.5 (e.g., 1.0) 0.21 LiCoO.sub.2 0.5 to 10.0 (e.g., 5.0)
2.80 Nickel seed 0.1 to 0.3 (e.g., 0.3) 0.27 1/2 cathode collector foil
1.5 and up (e.g., 6.25) 5.14 Totals (e.g., 53.1) 28.84 *In some embodiments,
the foils are about 0.5-mils (0.0005 inches = 12.52-microns) thick
In some embodiments, the cathode material layers 112 are each about 10
microns thick or more. In some embodiments, 10 microns of LiCoO.sub.2
provides about 0.552 mA-hour-per-square-cm per repeat unit 320 at 80%
theoretical utilization, and 2.1 mW-hour-per-square-cm at
3.8-volt-discharge voltage. In some embodiments, the charge-storage
density is about 104 mA-hour/cubic-cm, and about 19.1 Ahour/kg. In some
embodiments, the energy-storage density is about 395 W-hour/liter, and
about 72.8 W-hour/kg. In some embodiments, a 10-cm by 6.5-cm by one repeat
unit 320 corresponds to 33.6 mA-hour, and about 127 mW-hour. In some
embodiments, a final package measuring about 10.8-cm long by 6.5-cm wide
by 1.8-cm thick houses three sets of 320 repeat units each, the sets tied
in series to deliver 3.75 A-hour discharge from about 12.3 volts to about
9 volts.
FIG. 4 is a schematic cross-section view of a series-connected lithium
battery 400 of some embodiments of the invention. In the embodiment shown,
each sheet 126 has anode material covered with LiPON on one major face
(the upper face in FIG. 4) of the foil 125, and cathode material covered
with LiPON on the opposite major face (the lower face in FIG. 4). In some
embodiments, the outermost layers are single sided as shown, having a
metal face facing outwards. In other embodiments, all layers 125 are
identical one to another, including the outermost layers. In some
embodiments, the edge of the top-most layer 125 is electrically connected
(for example, on the right-hand side) to form external cathode
current-collector contact 421, and the edge of bottom-most layer 126 is
electrically connected (for example, on the left-hand side) to form
external anode current-collector contact 422, thus connecting all the
cells in series. Each repeat unit 420 shows one basic stack layer. Up to
one-A-hour or more single cells are thus formed, in some embodiments,
depending on the area of each cell.
FIG. 5A is a schematic cross-section view of a parallel-connected
screen-cathode-current -collector contact lithium-battery 500 of some
embodiments of the invention. This embodiment is substantially similar
to that of FIG. 3, except that, for the positive electrode, a metal
screening or mesh 510 replaces foil 110. In some embodiments, this allows
greater contact area to the cathode material 112, which is still
completely covered by LiPON layer 114. In some embodiments, metal
screening or mesh 510 is formed by selectively etching one or more
photo-lithographically-defined areas of a metal foil. In some embodiments,
LiCoO.sub.2 is sputtered onto the metal screening 510. In other
embodiments, a LiCoO.sub.2 powder is packed onto the screening 510. In
some embodiments, the LiCoO.sub.2 (whether deposited by sputtering
LiCoO.sub.2 or by packing LiCoO.sub.2 powder onto the screening 510) is
infused with polyPN or other polymer electrolyte material to enhance the
ionic conductivity within the cathode. In some embodiments, the screening
510 is initially (before depositing LiCoO.sub.2) about 50% open space,
and the open space is filled with LiCoO.sub.2 and/or polyPN or other
ionic-enhancement material.
In some embodiments, the metal screening or mesh 510 of all of the layers
511 are electrically connected to one another (for example, on the
right-hand side) to form external cathode current-collector contact 521,
and the edges of layers 120 are electrically connected to one another (for
example, on the left-hand side) to form external anode current-collector
contact 522, thus connecting all the cells in parallel. Each repeat unit
520 shows one basic stack layer.
TABLE-US-00003 TABLE 3 Materials List for FIG. 5A - 1 repeat unit Material
Thickness Layer Mass (microns) (mg/cm.sup.2) 1/2 cathode collector 1.5
and up (e.g., 6.25) 2.59 screen/mesh/etched foil LiCoO.sub.2 (cathode)
8.0 to 40 (e.g., 12.5) 7.00 LiPON (cathode protection and 0.1 to 2.5 (e.g.,
1.0) 0.21 electrolyte) soft polymer electrolyte and/or 0.5 to 10 (e.g.,
5.0) 0.75 "glue" LiPON (anode protection and 0.1 to 2.5 (e.g., 1.0) 0.21
electrolyte) Lithium (plated from LiCoO.sub.2) about 0.3 times 0.265
LiCoO.sub.2 thickness (e.g., 5.0) Copper (or Al, Ni, stainless steel, 0.1
to 1 (e.g., 0.25) 0.22 and the like) (used as the Li plate surface) Anode
collector foil 3 and up (e.g., 12.5 9.88 Copper (or Al, Ni, stainless steel,
0.1 to 1 (e.g., 0.25) 0.22 and the like) (used as the Li plate surface)
Lithium (plated from LiCoO.sub.2) about 0.3 times 0.265 LiCoO.sub.2
thickness (e.g., 5.0) LiPON (anode protection and 0.1 to 2.5 (e.g., 1.0)
0.21 electrolyte) soft polymer electrolyte and/or 0.5 to 10 (e.g., 5.0)
0.75 "glue" LiPON (cathode protection and 0.1 to 2.5 (e.g., 1.0) 0.21
electrolyte) LiCoO.sub.2 (cathode) 8.0 to 40 (e.g., 12.5) 7.00 1/2 cathode
collector 1.5 and up (e.g., 6.25) 2.59 screen/mesh/etched foil Totals
(e.g., 74.5) 32.37
In some embodiments, the cathode material layers include 31.25 microns
LiCoO.sub.2 in each repeat structure (50% of screen volume) at 80% packing,
and 95% electrical utilization corresponds to 1.63 mAhr/cm.sup.2/repeat
unit, and 6.22 mWhr/cm.sup.2/repeat unit at 3.8 V average discharge
voltage. In some embodiments, the LiCoO.sub.2 is infused with polyPN or
other polymer electrolyte material to enhance the ionic conductivity
within the cathode. In some embodiments, the charge storage density equals
218 mAhr/cm.sup.3; and 50.35 Ahr/kg. In some embodiments, the energy
storage density equals 835 Whr/liter, and 192 Whr/kg. In some embodiments,
each 10 cm.times.6.5 cm.times.1 repeat unit corresponds to 106 mAhr; 404
mWhr. In some embodiments, a final package 10.8 cm.times.6.5 cm.times.1.8
cm houses three sets of 80 repeat units each tied in series to deliver
8.5 Ahr in discharge from 12.3 V to 9 V.
FIG. 5B is a schematic cross-section view of a series-connected
screen-cathode-contact lithium-battery 501 of some embodiments of the
invention. This embodiment is substantially similar to that of FIG. 4,
except that a metal screening or mesh is laminated to the bottom side of
foil 535 (a foil corresponding to foil 110 of FIG. 4), or the bottom side
of foil 535 (starting with a foil 110 of FIG. 1A) is selectively etched
only part-way through to form a foil top side and a bottom side that has
a mesh-like quality. In some embodiments, this allows greater contact area
to the cathode material 112, which is still completely covered by LiPON
layer 114. In some embodiments, foil-mesh layer 535 is formed by
selectively etching a photolithographically-defined areas of a metal foil,
but not all the way through. In some embodiments, the outermost layers
are single sided as shown, having a metal face facing outwards. In other
embodiments, all layers 535 are identical one to another, including the
outermost layers (wherein the electrode layers facing outwards are
non-functioning). In some embodiments, the edge of the top-most layer 535
is electrically connected (for example, on the right-hand side) to form
external cathode current-collector contact 531, and the edge of
bottom-most layer 535 is electrically connected (for example, on the
left-hand side) to form external anode current-collector contact 532,
thus connecting all the cells in series. Each repeat unit 530 shows one
basic stack layer.
In some embodiments, the thin (0.1 to 1.0 micron) LiPON electrolyte serves
as a hard coating at the negative electrode preventing the formation of
lithium dendrites. Its use as a coating at the positive electrode (i.e.,
LiCoO.sub.2) doubly ensures that lithium plating at a defect site will
not short the battery. At both electrodes, LiPON also provides an
improvement in environmental resistance to water vapor and oxygen.
In some embodiments, the use of a relatively soft solid polymer
electrolyte (SPE) simplifies the construction of cells over a full
hard-electrolyte solid-state (e.g., LiPON only as the electrolyte) design.
The soft polymer electrolyte functions as an "electrolyte glue" that
allows the positive and negative electrodes to be constructed separately
and adhered to each other later in the assembly process. In some
embodiments, the soft polymer electrolyte is sprayed, squeegeed, or
otherwise deposited in liquid form, and later solidified.
Without the LiPON coating, some embodiments using a soft polymer
electrolyte would need sufficient soft polymer electrolyte thickness to
have mechanical rigidity or mechanical strength, which reduces energy
density and increases cell resistance. Without the soft polymer
electrolyte ("electrolyte glue"), LiPON films would need to be perfect
(defect free) over very large areas to achieve high-energy cells. The
combination of the two electrolyte material systems eliminates
shortcomings of either used alone.
Numerous metals can be used as the anode in battery cells of the present
invention. One common anode metal is lithium. The lithium must be
protected from oxygen and water vapor during manufacturing, assembly, and
use of the battery. Zinc is another common anode metal used in some
embodiments of the present invention. Zinc is the most electronegative
metal that has good stability and corrosion resistance, with the
appropriate inhibitor chemistry, in aqueous solutions. Several possible
metal-air systems are listed in Table 4 along with a summary of their
theoretical characteristics.
TABLE-US-00004 TABLE 4 Characteristics of metal-air cells. From "Handbook
of Batteries, 3.sup.rd Ed.," David Linden and Thomas B. Reddy, Eds., Table
38.2, McGraw-Hill Handbooks, New York, 2002. SUMMARY OF OTHER LITHIUM/AIR
RESEARCH Electrochemical Theoretical Theoretical Practical equivalent
cell specific energy operating Metal of metal, voltage, Valence (of metal),
voltage, anode Ah/g *V change kWh/kg V Li 3.86 3.4 1 13.0 2.4 Ca 1.34 3.4
2 4.6 2.0 Mg 2.20 3.1 2 6.8 1.2-1.4 Al 2.98 2.7 3 8.1 1.1-1.4 Zn 0.82 1.6
2 1.3 1.0-1.2 Fe 0.96 1.3 2 1.2 1.0 *Cell voltage with oxygen cathode
Lithium, the lightest alkali metal, has a unique place in battery systems.
Its gravimetric electrochemical equivalence of 3.86 amp-hrs/g is the
highest of any metallic anode material. It can be seen from Table 3 that
lithium has the highest operational voltage and greatest theoretical
specific energy of the metals listed. Using a lithium anode leads to a
very light, high energy density battery. The difficulty with lithium
technology is providing practical systems that operate in real world
conditions. It is possible to construct lithium cells utilizing an aqueous
electrolyte, but these cells have limited applicability due to corrosion
of the lithium metal anode by water. The lithium anode may also corrode
from contact with oxygen. A solution to the rapid corrosion of lithium
metal anodes in lithium-air cells includes the use of LiPON as a protective
barrier and separator in the structure of an organic-electrolyte lithium
cell.
In some embodiments, a cell utilizes a LiPON thin film acting as both a
portion of the electrolyte structure and a protective barrier against
moisture and oxygen corrosion of the lithium metal anode. The structure
of thin, flexible, lithium cells lends itself well to high-speed
web-deposition processes, as described in U.S. Pat. No. 6,805,998 (which
is incorporated herein by reference).
In some embodiments, a battery of the present invention (e.g., reference
numbers 100, 300, 400, 500, 600 or 900) is incorporated in an electrical
device such as a hearing aid, compass, cellular phone, tracking system,
scanner, digital camera, portable computer, radio, compact disk player,
cassette player, smart card, or other battery-powered device.
In some embodiments, the back (outside) of the cathode is exposed (or can
be exposed, for example, by removing a protective polymer film layer) to
air, such that oxygen acts as a cathode material. In some such embodiments,
the air cathode battery is a primary battery that cannot be recharged,
while in other embodiments, the air cathode battery is a secondary battery
that can be recharged.
Other Embodiments of the Invention
One aspect of the invention includes an apparatus including a lithium
anode covered by a LiPON electrolyte/protective layer, a
lithium-intercalation-material cathode covered by a LiPON
electrolyte/protective layer and a polymer electrolyte material
sandwiched between the LiPON electrolyte/protective layer that covers the
anode and the LiPON electrolyte/protective layer that covers the cathode.
In some embodiments, the cathode includes LiCoO.sub.2.
In some embodiments of the invention, the anode overlays a copper-anode
current-collector contact.
Another aspect of the invention includes a method including providing an
anode substrate having a conductive anode-current-collector contact
layer thereon, depositing a LiPON electrolyte/barrier layer over the
anode-current-collector contact layer, providing a polymer electrolyte,
and providing a cathode substrate having a cathode-current-collector
contact layer, depositing a lithium intercalation material on the cathode
current-collector contact layer, depositing a LiPON electrolyte/barrier
layer over the cathode-current-collector contact layer, and forming a
sandwich of the anode substrate and the cathode substrate with the polymer
electrolyte therebetween. In some embodiments, a structure is provided
having a plurality of anode substrates and a plurality of cathode
substrates with polymer electrolyte between each pair of anode and cathode
substrates.
Another aspect of the invention includes an apparatus that includes a
substrate having an anode current-collector contact, a LiPON electrolyte
separator deposited on the anode current-collector contact, and a plated
layer of lithium anode material between the LiPON and the anode
current-collector contact.
In some embodiments, the anode current-collector contact includes copper
and the substrate includes a polymer.
Another aspect of the invention includes an apparatus including a
deposition station that deposits LiPON onto an anode current-collector
contact, a plating station that plates lithium onto the anode
current-collector contact to form an anode substrate, a
cathode-deposition station that deposits a cathode material onto a
substrate and deposits LiPON onto the cathode material to form a cathode
substrate, and an assembly station that assembles the anode substrate to
the cathode substrate using a polymer electrolyte material sandwiched
between the cathode substrate and the anode substrate.
In some embodiments of the invention, the deposition station comprises
sputter deposition of LiPON.
In some embodiments, the LiPON is deposited onto the anode
current-collector contact with a thickness of between about 0.1 microns
and about 1 micron. In some embodiments, the anode's LiPON layer is less
than 0.1 microns thick. In some embodiments, this LiPON layer is about
0.1 microns. In some embodiments, this LiPON layer is about 0.2 microns.
In some embodiments, this LiPON layer is about 0.3 microns. In some
embodiments, this LiPON layer is about 0.4 microns. In some embodiments,
this LiPON layer is about 0.5 microns. In some embodiments, this LiPON
layer is about 0.6 microns. In some embodiments, this LiPON layer is about
0.7 microns. In some embodiments, this LiPON layer is about 0.8 microns.
In some embodiments, this LiPON layer is about 0.9 microns. In some
embodiments, this LiPON layer is about 1.0 microns. In some embodiments,
this LiPON layer is about 1.1 microns. In some embodiments, this LiPON
layer is about 1.2 microns. In some embodiments, this LiPON layer is about
1.3 microns. In some embodiments, this LiPON layer is about 1.4 microns.
In some embodiments, this LiPON layer is about 1.5 microns. In some
embodiments, this LiPON layer is about 1.6 microns. In some embodiments,
this LiPON layer is about 1.7 microns. In some embodiments, this LiPON
layer is about 1.8 microns. In some embodiments, this LiPON layer is about
1.9 microns. In some embodiments, this LiPON layer is about 2.0 microns.
In some embodiments, this LiPON layer is about 2.1 microns. In some
embodiments, this LiPON layer is about 2.2 microns. In some embodiments,
this LiPON layer is about 2.3 microns. In some embodiments, this LiPON
layer is about 2.4 microns. In some embodiments, this LiPON layer is about
2.5 microns. In some embodiments, this LiPON layer is about 2.6 microns.
In some embodiments, this LiPON layer is about 2.7 microns. In some
embodiments, this LiPON layer is about 2.8 microns. In some embodiments,
this LiPON layer is about 2.9 microns. In some embodiments, this LiPON
layer is about 3 microns. In some embodiments, this LiPON layer is about
3.5 microns. In some embodiments, this LiPON layer is about 4 microns.
In some embodiments, this LiPON layer is about 4.5 microns. In some
embodiments, this LiPON layer is about 5 microns. In some embodiments,
this LiPON layer is about 5.5 microns. In some embodiments, this LiPON
layer is about 6 microns. In some embodiments, this LiPON layer is about
7 microns. In some embodiments, this LiPON layer is about 8 microns. In
some embodiments, this LiPON layer is about 7 microns. In some embodiments,
this LiPON layer is about 9 microns. In some embodiments, this LiPON layer
is about 10 microns. In some embodiments, this LiPON layer is more than
10 microns.
In some embodiments, the LiPON is deposited onto the cathode
current-collector contact with a thickness of between about 0.1 microns
and about 1 micron. In some embodiments, the cathode's LiPON layer is less
than 0.1 microns thick. In some embodiments, this UPON layer is about 0.1
microns. In some embodiments, this LiPON layer is about 0.2 microns. In
some embodiments, this UPON layer is about 0.3 microns. In some
embodiments, this LiPON layer is about 0.4 microns. In some embodiments,
this LiPON layer is about 0.5 microns. In some embodiments, this LiPON
layer is about 0.6 microns. In some embodiments, this LiPON layer is about
0.7 microns. In some embodiments, this LiPON layer is about 0.8 microns.
In some embodiments, this LiPON layer is about 0.9 microns. In some
embodiments, this LiPON layer is about 1.0 microns. In some embodiments,
this LiPON layer is about 1.1 microns. In some embodiments, this LiPON
layer is about 1.2 microns. In some embodiments, this LiPON layer is about
1.3 microns. In some embodiments, this LiPON layer is about 1.4 microns.
In some embodiments, this LiPON layer is about 1.5 microns. In some
embodiments, this LiPON layer is about 1.6 microns. In some embodiments,
this UPON layer is about 1.7 microns. In some embodiments, this LiPON layer
is about 1.8 microns. In some embodiments, this LiPON layer is about 1.9
microns. In some embodiments, this LiPON layer is about 2.0 microns. In
some embodiments, this LiPON layer is about 2.1 microns. In some
embodiments, this LiPON layer is about 2.2 microns. In some embodiments,
this LiPON layer is about 2.3 microns. In some embodiments, this LiPON
layer is about 2.4 microns. In some embodiments, this LiPON layer is about
2.5 microns. In some embodiments, this LiPON layer is about 2.6 microns.
In some embodiments, this LiPON layer is about 2.7 microns. In some
embodiments, this LiPON layer is about 2.8 microns. In some embodiments,
this LiPON layer is about 2.9 microns. In some embodiments, this LiPON
layer is about 3 microns. In some embodiments, this LiPON layer is about
3.5 microns. In some embodiments, this LiPON layer is about 4 microns.
In some embodiments, this LiPON layer is about 4.5 microns. In some
embodiments, this LiPON layer is about 5 microns. In some embodiments,
this LiPON layer is about 5.5 microns. In some embodiments, this LiPON
layer is about 6 microns. In some embodiments, this LiPON layer is about
7 microns. In some embodiments, this LiPON layer is about 8 microns. In
some embodiments, this LiPON layer is about 7 microns. In some embodiments,
this LiPON layer is about 9 microns. In some embodiments, this LiPON layer
is about 10 microns. In some embodiments, this LiPON layer is more than
10 microns.
In some embodiments, the plating station performs electroplating at
densities of about 0.9 mA/cm.sup.2 and voltage of about 40 mV at 0.6 mA
between a lithium counterelectrode and the plated lithium of the anode.
In some embodiments of the invention, during a precharge of the anode,
the lithium is conducted through a liquid propylene carbonate/LiPF.sub.6
(or other suitable lithium salt) electrolyte solution and the LiPON
barrier/electrolyte layer for the lithium to be wet-bath plated onto the
anode connector or conduction layer (e.g., copper foil or a copper layer
on an SiO.sub.2 or polymer substrate.
FIG. 6A is a perspective view of an electrode 600 having a
hard-electrolyte-covered current collector with a plating mask 119. In
some embodiments, a starting substrate such as 721 shown in FIG. 7B has
its metal layer 720 (e.g., copper) photolithographically defined to form
patterned metal layer 620 having contact pad 629, used for plating (such
as shown in FIG. 6C) and for connecting to the external electrical
conductor in the finished battery. In some embodiments, on top of
patterned metal layer 620 is a patterned (e.g., photolithographically)
hard electrolyte layer 624 (e.g., such as a hard electrolyte layer 124
described in FIG. 1C, but with some of its lateral edges removed). In some
embodiments, an optional mask layer 119 is formed and/or patterned over
the metal via between the main body of patterned metal layer 620 (which
will be plated with lithium through patterned hard electrolyte layer 624
(e.g., LiPON)). In some embodiments, mask 119 prevents lithium from
plating on the via, thus leaving sealed the interface between patterned
hard electrolyte layer 624 and the metal via (otherwise, water vapor or
air could cause the lithium plated in this area to corrode, leaving a gap
that could cause more corrosion of the main body of the lithium on
patterned metal layer 620. Because the patterned hard electrolyte layer
624 extends laterally beyond the lateral extent of patterned metal layer
620 on the rest of its periphery, no mask is required in those areas, since
the lithium will not plate there and the sealed interface between
patterned hard electrolyte layer 624 and the underlying non-conductive
substrate remains intact and sealed.
FIG. 6B is a perspective view of another electrode 601 having a
hard-electrolyte-covered current collector with a plating mask 119. In
some embodiments such as shown here, the entire substrate surface is metal,
so a mask 119 is deposited and/or patterned over the outer periphery of
hard electrolyte layer 124 (e.g., LiPON), mask 119 with an interior
opening 129 through which lithium will plate through the LiPON layer 124
to most of the central portion of the face of substrate 120 (e.g., a metal
foil). In some embodiments, mask 119 is a photoresist layer that is
patterned and left in place during plating. In other embodiments, mask
119 is another material (such as deposited SiO.sub.2) that is patterned
using photoresist, which is then removed. In still other embodiments, mask
119 is a material (such as SiO.sub.2) that is deposited directly on the
metal substrate 120, and is patterned using photoresist that is then
removed before deposition of the hard electrolyte layer 124 (e.g., LiPON),
thus preventing lithium from plating around the periphery (i.e., the mask
119 is under the LiPON, in some embodiments).
FIG. 6C is a perspective view of a plating system 610. In some embodiments,
one or more electrodes 600 and/or electrodes 601 are partially or
completely submerged in a liquid electrolyte 606 (e.g., propylene
carbonate and/or ethylene carbonate with dissolved LiPF.sub.6 or other
suitable electrolyte). In some embodiments, a sacrificial block of
lithium 605 is kept submerged in the electrolyte 606, and a suitable
plating voltage is applied between the lithium block 605 and electrode(s)
600 and/or 601. In some embodiments, the contact pad 629 is kept out of
the liquid to prevent lithium from plating there.
FIGS. 7A, 7B, 7C, 7D, 7E, and 7F are schematic cross-sectional views of
the fabrication (shown as a series 700 of operations) of an atomic level
matrix of copper and copper oxides as cathodes on a substrate of some
embodiments of the invention. FIG. 7A shows a cross-section view of the
starting substrate 710 (e.g., silicon, alumina, stainless steel, aluminum,
or polymer, or a composite of different materials). In some embodiments,
an aluminum-foil substrate (or other metal that could spontaneously alloy
with lithium and thereby degrade performance of the battery) or an
insulator or non-conductor (such as silicon or polymer, which does not
conduct the electricity from the battery) is coated with copper or nickel
(or other metal that conducts electricity and does not readily alloy with
lithium and thereby helps maintain performance of the battery).
In some embodiments, a cathode starting material contains no lithium (e.g.,
a copper foil, screening, or insulator coated with a copper conduction
layer, then coated with a high-surface area carbon or Cu.sub.xO.sub.x
(which has a high volumetric energy density) or other material useful as
a lithium-battery electrode, optionally infused with polyPN). In some
embodiments, (see FIG. 7B) a metal layer 720 (e.g., copper, nickel, or
other suitable metal that does not readily alloy with lithium during
charging or discharging of the battery) is deposited (e.g., by sputtering
copper with no oxygen) on one or more major faces (e.g., the top and/or
bottom surfaces shown in the figures) of a substrate 710 (e.g., a silicon
wafer optionally having an SiO.sub.2 insulation layer on one or both sides,
an alumina or glass wafer, or a polymer film), to form a metal-coated
substrate 721. In some embodiments, metal-coated substrate 721 can be used
as the current collector base (rather than metal foil 111 or 121) for
either the anode or cathode of any of the above-described embodiments.
In some embodiments, the starting substrate includes a plurality of metal
layers (e.g., aluminum or copper moisture-barrier layers) alternating
with a smoothing layer (e.g., spun-on photoresist or polyurethane)
between each pair of metal layers to form a barrier stack (e.g., see U.S.
patent application Ser. No. 11/031,217 filed Jan. 6, 2005, entitled
"LAYERED BARRIER STRUCTURE HAVING ONE OR MORE DEFINABLE LAYERS AND METHOD",
which is incorporated herein by reference), wherein the top-most metal
layer of this stack is a metal that (unlike aluminum) does not readily
alloy with lithium during battery charging or discharging (e.g., a metal
such as copper). Such a moisture-barrier stack is particularly useful for
sealing a substrate that transmits some moisture and/or oxygen over time
(e.g., a polymer film substrate such as polyethylene or Kapton.TM.), where
the barrier stack.
For some embodiments using a lithium-free starting cathode, copper is then
is sputtered in a partial O.sub.2 atmosphere onto metal-coated substrate
721 (in some embodiments, the concentration of oxygen is increased over
time such that the first material deposited is mostly copper, and
gradually the material includes more and more oxygen in the
copper-copper-oxide matrix) in argon (e.g., forming an atomic-scale
mixture of copper, Cu.sub.4O in layer 722 (see FIG. 7C), Cu.sub.2O in layer
724 (see FIG. 7D), Cu.sup.+O.sup.- and/or CuO in layer 728 (see FIG. 7E),
or a succession of the copper substrate 720, then mostly Cu.sub.4O in layer
722, then mostly Cu.sub.2O in layer 724, then Cu.sup.+O.sup.- and then
CuO in layer 728 and/or an atomic-scale matrix of copper and copper oxides).
In some embodiments, a layer of hard electrolyte 714 (see FIG. 7F), such
as LiPON, is deposited across the finished cathode material.
FIGS. 8A, 8B, 8C, 8D, and 8E are schematic cross-sectional views of the
fabrication (shown as a series 800 of operations) of an atomic level matrix
of copper and copper oxides as cathodes on a copper-foil substrate of some
embodiments of the invention. In some embodiments, (see FIG. 8A) a copper
foil 711 or film is the starting material. In some embodiments, the
starting foil is sputtered with argon to clean the surface(s) to be used
for cathodes (e.g., the top and/or bottom surfaces shown), then copper
is sputtered in a partial O.sub.2 atmosphere (in some embodiments, the
concentration of oxygen is increased over time such that the first
material deposited is mostly copper, and gradually the material includes
more and more oxygen in the copper-copper-oxide matrix) in argon (e.g.,
forming an atomic-scale mixture of copper, Cu.sub.4O 722 (see FIG. 8B),
Cu.sub.2O 724 (see FIG. 8C), Cu.sup.+O.sup.- and/or CuO 728 (see FIG. 8D),
or a succession of the copper substrate 720, then mostly Cu.sub.4O 722,
then mostly Cu.sub.2O 724, then Cu.sup.+O.sup.- and then CuO 728 and/or
an atomic-scale matrix of copper and copper oxides). In some embodiments,
a layer of hard electrolyte 714 (see FIG. 8E) such as LiPON is deposited
across the finished cathode material.
In some such embodiments, the copper metal spreads through the copper
oxides (which intercalate lithium, in some embodiments), providing better
electrical conductivity as the lithium migrates in and out of the cathode.
In some embodiments, the anode is precharged by electroplating lithium
through the LiPON electrolyte that has been deposited thereon.
In other embodiments, one or more copper oxides and/or copper powder are
powder-pressed onto a copper substrate or screen (i.e., the cathode
conduction layer). In still other embodiments, an ink, having one or more
copper oxides and/or copper powder, is printed, sprayed, doctor-bladed,
or otherwise deposited on the cathode conduction layer. In some
embodiments of the invention, the cathode material is charged with lithium
that is conducted through a liquid propylene carbonate/LiPF.sub.6
electrolyte solution and the LiPON barrier/electrolyte layer for the
lithium to be plated onto/into the cathode material and/or connector or
conduction layer.
FIG. 9 is a schematic cross-section view of a parallel-connected
foil-substrate-cathode -current-collector contact thin-film battery 900
of some embodiments of the invention. Battery 900 includes two cells
connected in parallel, where two-sided anode current collector 120 has
anode material 122 (e.g., lithium metal) that has been electroplated
through hard electrolyte layers 124 (e.g., LiPON) on both sides of central
current collector layer 120 (e.g., a metal foil or metal-coated polymer
film), as defined by masks 119. In some embodiments, two cathode current
collectors 110 each have cathode material 112 (e.g., LiCoO.sub.2)
deposited and photolithographically patterned and covered with hard
electrolyte layers 124 (e.g., LiPON). Pinhole 992 in hard electrolyte
layer 124 and/or pinhole 991 in hard electrolyte layer 124 would cause
failures of a typical single-layer electrolyte battery, but in the present
invention, the pinholes do not align (e.g., vertically in the figure) with
one another, and, in some embodiments, are filled with the soft polymer
electrolyte 130, which acts to fill such holes and automatically "heal"
the battery. Other details of this battery are as described above for FIG.
3.
FIG. 10A is a schematic cross-section view of an encapsulated
surface-mount single-cell micro-battery device 1000 of some embodiments
of the invention (other embodiments use stacks of cells as described
above). In some embodiments, a silicon wafer substrate has a plurality
of such cells fabricated on it, and is diced apart to form silicon
substrate 1011 having a metal current collector 1010 on its surface, which
then has cathode material 112 and hard electrolyte layer 114 deposited
thereon to form the cathode component. A foil anode component having foil
substrate 120, anode metal 122, and hard electrolyte layer 124 is then
laminated to the cathode component using a soft polymer electrolyte glue
130. This battery is then connected to a lead frame having cathode
connector 1051 and anode connector 1052 and encapsulated in encapsulant
material 1050, and the leads formed as gull-wing leads as shown or bent
into J-shaped leads that curl under the package. Surface-mount-device
1000 can then be soldered to a circuit board to provide small amounts of
battery power to other components on the circuit board (such as real-time
clocks or timers, or static random-access memories, RFID circuits, and
the like). In other embodiments, a plurality of foil battery cells is used
instead and encapsulated to form a surface-mount chip-like battery having
higher current and/or higher voltage capabilities.
FIG. 10B is a perspective view of the outside of encapsulated
surface-mount micro-battery device 1000 (described above in FIG. 10A),
of some embodiments of the invention. In some embodiments, a stack of foil
battery cells (e.g., such as those described in FIG. 3, FIG. 4, FIG. 5A,
and/or FIG. 5B, and, in some embodiments, with or without a silicon wafer
substrate) is encapsulated in this form factor to create a surface-mount
chip-like battery having higher current and/or higher voltage
capabilities.
FIG. 11 is a flow chart of a method 1100 for making a battery cell according
to some embodiments of the invention. In some embodiments, method 1100
includes providing 1110 a first sheet (e.g., 121) that includes an anode
material and a hard electrolyte layer covering the anode material,
providing 1112 a second sheet (e.g., 111) having a cathode material and
a hard electrolyte layer covering the cathode material, and sandwiching
1114 a soft (e.g., polymer) electrolyte material between the hard
electrolyte layer of the first sheet and the hard electrolyte layer of
the second sheet. Some embodiments of the method 1100 further include the
functions shown in FIG. 12.
FIG. 12 is a flow chart of a method 1200 for making a stacked battery
according to some embodiments of the invention. In some embodiments,
method 1200 includes performing 1210 the method 1100 of FIG. 11, providing
1212 a third sheet that includes an anode material and a hard electrolyte
layer covering the anode material, providing a fourth sheet that includes
a cathode material and a hard electrolyte layer covering the cathode
material, sandwiching 1216 a polymer electrolyte material between the
hard electrolyte layer covering the anode material of the third sheet and
the hard electrolyte layer covering the cathode material of the fourth
sheet, and between the hard electrolyte layer covering the anode material
of the first sheet and the hard electrolyte layer covering the cathode
material of the fourth sheet.
FIG. 13 is a perspective exploded view of information-processing system
1300 (such as a laptop computer) using battery device 1330 (which, in
various embodiments, is any one or more of the battery devices described
herein). For example, in various exemplary embodiments,
information-processing system 1300 embodies a computer, workstation,
server, supercomputer, cell phone, automobile, washing machine,
multimedia entertainment system, or other device. In some embodiments,
packaged circuit 1320 includes a computer processor that is connected to
memory 1321, power supply (energy-storage device 1330), input system 1312
(such as a keyboard, mouse, and/or voice-recognition apparatus),
input-output system 1313 (such as a CD or DVD read and/or write apparatus),
input-output system 1314 (such as a diskette or other magnetic media
read/write apparatus), output system 1311 (such as a display, printer,
and/or audio output apparatus), wireless communication antenna 1340, and
packaged within enclosure having a top shell 1310, middle shell 1315, and
bottom shell 1316. In some embodiments, energy-storage device 1330 is
deposited (e.g., as vapors forming thin-film layers in a vacuum deposition
station) or laminated (as partially assembled electrode films) as
thin-film layers directly on and substantially covering one or more
surfaces of the enclosure (i.e., top shell 1310, middle shell 1315, and/or
bottom shell 1316).
FIG. 14 shows an information-processing system 1400 having a similar
configuration to that of FIG. 13. In various exemplary embodiments,
information-processing system 1400 embodies a pocket computer, personal
digital assistant (PDA) or organizer, pager, Blackberry.TM.-type unit,
cell phone, GPS system, digital camera, MP3 player-type entertainment
system, and/or other device. In some embodiments, packaged circuit 1420
includes a computer processor that is connected to memory 1421,
power-supply battery device 1430, input system 1412 (such as a keyboard,
joystick, and/or voice-recognition apparatus), input/output system 1414
(such as a portable memory card connection or external interface), output
system 1411 (such as a display, printer, and/or audio output apparatus),
wireless communication antenna 1440, and packaged within enclosure having
a top shell 1410 and bottom shell 1416. In some embodiments, battery device
1430 (which, in various embodiments, is any one or more of the battery
devices described herein) is deposited as film layers directly on and
substantially covering one or more surfaces of the enclosure (i.e., top
shell 1410 and/or bottom shell 1416).
In some embodiments, at least one of the hard electrolyte layers is a
glass-like layer that conducts lithium ions. In some such embodiments,
at least one of the hard electrolyte layers includes LiPON. In some
embodiments, the first hard electrolyte layer and the second hard
electrolyte layer are both LiPON. In some such embodiments, each of the
hard electrolyte layers is formed by sputtering from a LiPON source onto
substrates having one or more electrode materials. In some such
embodiments, each of the hard electrolyte layers is formed by sputtering
from a lithium phosphate source in a nitrogen atmosphere onto substrates
having one or more electrode materials. In some embodiments, each of the
hard electrolyte layers is formed by sputtering from a lithium phosphate
source in a nitrogen atmosphere, using an ion-assist voltage, onto
substrates having one or more electrode materials.
In some embodiments, the soft electrolyte layer includes one or more
polymers having a gel-like consistency at room temperatures.
In some embodiments, the soft layer includes a polyphosphazene polymer.
In some such embodiments, the soft layer includes co-substituted linear
polyphosphazene polymers. In some such embodiments, the soft layer
includes polyphosphazene polymers having a gel-like consistency at room
temperatures. In some such embodiments, the soft layer includes MEEP
(poly[bis(2-(T-methoxyethoxy ethoxy)phosphazene]).
In some embodiments, the soft-electrolyte layer is formed by depositing
soft-electrolyte material onto the hard-electrolyte layer on the positive
electrode, depositing soft-electrolyte material onto the
hard-electrolyte layer on the negative electrode, and pressing the
soft-electrolyte material on the positive electrode and the
soft-electrolyte material on the negative electrode against each other.
In some embodiments, the soft layer includes a polymer matrix infused with
a liquid and/or gel electrolyte material (e.g., polyPN). In some such
embodiments, the polymer matrix is formed by waffle embossing
(micro-embossing to leave raised structures, e.g., about 0.1 microns high
to about 5 microns high: in some embodiments, about 0.1 microns, about
0.2 microns, about 0.3 microns, about 0.4 microns, about 0.5 microns,
about 0.6 microns, about 0.7 microns, about 0.8 microns, about 0.9 microns,
about 1.0 microns, about 1.2 microns, about 1.4 microns, about 1.6 microns,
about 1.8 microns, about 2.0 microns, about 2.2 microns, about 2.4 microns,
about 2.6 microns, about 2.8 microns, about 3.0 microns, about 3.5 microns,
about 4 microns, about 4.5 microns, about 5 microns, about 6 microns, about
7 microns, about 8 microns, about 9 microns, or about 10 microns high)
a heated polymer material onto at least one of the positive electrode and
the negative electrode. In some such embodiments, the waffle embossing
forms a pattern of dots. In some such embodiments, the waffle embossing
forms a pattern of lines. In some such embodiments, the waffle embossing
forms a two-directional/two-dimensional pattern of lines (e.g., in some
embodiments, intersecting lines forming squares, triangles, hexagons,
and/or the like, while in other embodiments, non-intersecting geometric
patterns such as circles, squares, triangles, and/or the like). In other
embodiments, a one-directional pattern of lines is microembossed in one
direction on the positive electrode and in another direction on the
negative electrode.
In some embodiments, the soft electrolyte layer includes a thin (e.g.,
0.5 to 5.0 microns thick) polymer sponge or screen (e.g., a polypropylene
sponge) infused with a liquid and/or gel electrolyte material (e.g.,
polyPN) and placed between the two hard electrolyte layers.
In some such embodiments, the soft-electrolyte layer is formed by
depositing a thin soft-electrolyte layer onto the hard electrolyte layer
on the positive electrode, depositing a thin soft-electrolyte layer onto
the hard electrolyte layer on the negative electrode, and pressing the
soft electrolyte layer on the positive electrode and the soft electrolyte
layer on the negative electrode against each other. In some such
embodiments, at least one of the thin soft-electrolyte layers is formed
by doctor blading. In some such embodiments, at least one of the thin
soft-electrolyte layers is formed by spraying. In some such embodiments,
at least one of the thin soft-electrolyte layers is formed by
silk-screening. In some such embodiments, at least one of the thin
soft-electrolyte layers is formed by printing.
In some embodiments, the battery includes a positive electrode that
includes a LiCoO.sub.2 layer deposited on a copper current-collector
layer, about 1 micron of LiPON deposited on the LiCoO.sub.2 layer, a layer
of between about 1 micron and three microns of
polyphosphazene/lithium-salt electrolyte material, and about 1 micron of
LiPON on the negative electrode. In some embodiments, the negative
electrode includes a copper current collector onto which LiPON is
deposited and that is precharged by wet plating lithium onto the copper
current collector through the LiPON layer. In some embodiments, the layer
of polyphosphazene/lithium-salt electrolyte material is formed by
depositing about 1 micron of polyphosphazene/lithium-salt electrolyte
material on the LiPON deposited on the positive electrode, depositing
about 1 micron of polyphosphazene/lithium-salt electrolyte material on
the LiPON on the negative electrode and contacting the
polyphosphazene/lithium-salt electrolyte material on the positive
electrode to the polyphosphazene/lithium-salt electrolyte material on
the negative electrode. In some such embodiments, the contacting includes
pressing between rollers.
Some embodiments of the invention include an apparatus that includes a
battery cell having a positive electrode, a negative electrode, and an
electrolyte structure therebetween, wherein the electrolyte structure
includes a soft electrolyte layer and at least one hard electrolyte layer.
In some embodiments, the electrolyte structure includes a hard
electrolyte layer on the negative electrode, and the soft electrolyte
layer is sandwiched between the positive electrode and the hard
electrolyte layer on the negative electrode. In some such embodiments,
the invention omits the hard electrolyte covering on the positive
electrode.
In some embodiments, the soft electrolyte layer includes a
polyphosphazene. In some embodiments, the soft electrolyte layer includes
MEEP. In some embodiments, the soft electrolyte layer also includes a
metal salt, such as LiPF6, LiBF4, LiCF3SO4, CF3SO3Li (lithium
trifluoromethanesulfonate, also called triflate), lithium
bisperfluoroethanesulfonimide, lithium (Bis)
Trifluoromethanesulfonimide, or the like or a mixture or two or more such
salts, for example.
In some embodiments, the electrolyte structure includes a hard
electrolyte layer on the positive electrode and a hard electrolyte layer
on the negative electrode, and the soft electrolyte layer is sandwiched
between the hard electrolyte layer on the positive electrode and the hard
electrolyte layer on the negative electrode. In some embodiments, the
thicknesses of the hard electrolyte layer on the positive electrode and
of the hard electrolyte layer on the negative electrode are each about
one micron or less. In some embodiments, the thicknesses of the hard
electrolyte layer on the positive electrode and of the hard electrolyte
layer on the negative electrode are each about 0.5 microns or less. In
some embodiments, the thickness of the soft electrolyte layer is about
three microns or less. In some embodiments, the thickness of the soft
electrolyte layer is about two microns or less. In some embodiments, the
thickness of the soft electrolyte layer is about one micron or less.
In some embodiments, the hard electrolyte layer on the positive electrode
includes is substantially the same material as the hard electrolyte layer
on the negative electrode. In some embodiments, the hard electrolyte layer
on the positive electrode includes is substantially the same thickness
as the hard electrolyte layer on the negative electrode.
In some embodiments, the hard electrolyte layer on the positive electrode
includes LiPON and the hard electrolyte layer on the negative electrode
includes UPON.
In some embodiments, the soft electrolyte layer includes a gel.
In some embodiments, the soft electrolyte layer includes a gel that
includes a polyvinylidene difluoride (PVdF), propylene carbonate, and a
lithium salt. PVdF is a polymer that does not conduct lithium ions, that
is, lithium salts will not dissolve in PVdF. However, PVdF can be swollen
with a liquid such as propylene carbonate in which a lithium salt has been
dissolved. The gel that results can be used as a soft electrolyte.
Some embodiments further include an encapsulating material surrounding
the battery cell, and one or more electrical leads connecting from the
battery cell to an exterior of the encapsulating material.
Some embodiments further include an electronic device and a housing
holding the electrical device, wherein the battery cell is within the
housing and supplies power to the electronic device.
Some embodiments of the invention include a method that includes providing
a positive electrode component, providing a negative electrode component,
coating at least the negative electrode component with a hard electrolyte
layer, and forming a battery cell using the positive electrode component,
the negative electrode component that is coated with the hard electrolyte
layer, and a soft electrolyte layer in between.
Some embodiments of the method further include coating the positive
electrode component with a hard electrolyte layer, wherein an electrolyte
structure of the battery cell includes the hard electrolyte layer on the
negative electrode, the hard electrolyte layer on the positive electrode,
and the soft electrolyte layer which is sandwiched between the hard
electrolyte layer on the positive electrode and the hard electrolyte layer
on the negative electrode.
In some embodiments of the method, the electrolyte structure includes a
hard electrolyte layer on the positive electrode and a hard electrolyte
layer on the negative electrode, and the soft electrolyte layer is
sandwiched between the hard electrolyte layer on the positive electrode
and the hard electrolyte layer on the negative electrode.
In some embodiments of the method, the hard electrolyte layer on the
positive electrode includes LiPON and the hard electrolyte layer on the
negative electrode includes LiPON.
In some embodiments of the method, the soft electrolyte layer includes
a polyphosphazene and a lithium salt. In some embodiments, the soft
electrolyte layer includes MEEP and a lithium salt. In some embodiments,
the lithium salt includes LiPF6, LiBF4, LiCF3SO4, CF3SO3Li (lithium
trifluoromethanesulfonate, also called triflate), lithium
bisperfluoroethanesulfonimide, lithium (Bis)
Trifluoromethanesulfonimide, or the like or a mixture or two or more such
salts, for example.
Some embodiments of the invention include an apparatus that includes a
positive electrode component coated with a hard electrolyte layer, a
negative electrode component coated with a hard electrolyte layer, and
electrolyte means for connecting the hard electrolyte layer on the
negative electrode component to the hard electrolyte layer on the positive
electrode component to form a battery cell.
In some embodiments, the means for connecting further includes means for
fixing defects in one or more of the hard electrolyte layers.
In some embodiments, the hard electrolyte layer on the positive electrode
includes LiPON and the hard electrolyte layer on the negative electrode
includes LiPON.
In some embodiments, the means for connecting includes MEEP. In some
embodiments, the means for connecting includes a polyphosphazene and a
lithium salt. In some embodiments, the means for connecting includes MEEP
and a lithium salt. In some embodiments, the lithium salt includes LiPF6,
LiBF4, LiCF3SO4, CF3SO3Li (lithium trifluoromethanesulfonate, also
called triflate), lithium bisperfluoroethanesulfonimide, lithium (Bis)
Trifluoromethanesulfonimide, or the like or a mixture or two or more such
salts, for example.
Some embodiments further include an encapsulating material surrounding
the battery cell, and one or more electrical leads connecting from the
battery cell to an exterior of the encapsulating material.
Some embodiments further include an electronic device, wherein the
battery cell supplies power to at least a portion of the electronic device.
Some embodiments of the invention include an apparatus that includes a
first battery cell having a negative electrode, a positive electrode, and
an electrolyte structure, wherein the negative electrode includes an
anode material and a LiPON layer covering at least a portion of the
negative electrode, the positive electrode includes a cathode material
and a UPON layer covering at least a portion of the positive electrode,
and the electrolyte structure includes a polymer electrolyte material
sandwiched between the LiPON layer of the negative electrode and the LiPON
layer of the positive electrode.
In some embodiments, the cathode material includes LiCoO2 that is
deposited on a positive electrode current-collector material, and the
LiPON layer of the positive electrode is deposited on the LiCoO2. In some
such embodiments, the positive electrode current-collector contact
material includes a metal mesh around which the cathode material is
deposited.
In some embodiments, the negative electrode includes a negative-electrode
current collector made of a metal that does not readily alloy with lithium
during a plating operation, and lithium metal is plated onto the
negative-electrode current collector through the LiPON layer covering the
negative electrode. In some such embodiments, the metal of the
negative-electrode current collector includes copper. In some such
embodiments, the negative electrode includes a mask layer covers a
periphery of the negative-electrode current collector and lithium metal
is plated through the LiPON layer covering the negative electrode onto
an area of the metal negative-electrode current collector defined by the
mask.
In some embodiments, the negative electrode includes a current-collector
metal layer, and the anode material includes lithium metal deposited on
at least one of two major faces of the metal layer that is at least
partially covered by the LiPON layer of the negative electrode.
In some embodiments, the anode material is deposited on both major faces
of the metal layer of the negative electrode, each face at least partially
covered by the LiPON layer of the negative electrode.
In some embodiments, the positive electrode includes a current-collector
metal layer, and the cathode material is deposited on both major faces
of the metal layer and is at least partially covered by the LiPON layer.
In some embodiments, the negative electrode includes a current-collector
metal layer, and the anode material includes lithium metal plated onto
both major faces of the negative-electrode current-collector metal layer
through the LiPON layer covering the negative electrode.
In some embodiments, the negative electrode includes a current-collector
contact foil coated with the LiPON layer of the negative electrode, the
lithium anode material includes lithium metal plated onto a first major
face of the current-collector contact foil through the LiPON layer
covering the current-collector contact foil, the lithium cathode material
of a second battery cell is deposited onto a second major face of the
current-collector contact foil of the negative electrode of the first
battery cell, and the LiPON barrier/electrolyte layer covering the
cathode material of the second battery cell is then deposited by
sputtering.
In some embodiments, the positive electrode includes a current-collector
foil, the lithium cathode material is deposited onto both major faces of
the positive electrode current-collector contact foil, and the LiPON
barrier/electrolyte layer covering the positive electrode is then
deposited by sputtering.
In some embodiments, the positive electrode includes a current-collector
contact mesh, the lithium cathode material is deposited onto both major
faces of the cathode current-collector contact mesh, and the LiPON
barrier/electrolyte layer covering the positive electrode is then
deposited by sputtering.
Some embodiments of the invention include a method that includes providing
a first sheet that includes an anode material and a LiPON
barrier/electrolyte layer covering the anode material, providing a second
sheet that includes a cathode material that includes lithium and a LiPON
barrier/electrolyte layer covering the cathode material, and sandwiching
a polymer electrolyte material between the LiPON barrier/electrolyte
layer covering the anode material of the first sheet and the LiPON
barrier/electrolyte layer covering the cathode material of the first
cathode sheet.
Some embodiments of the method further include providing a third sheet
that includes an anode material and a LiPON barrier/electrolyte layer
covering the anode material, providing a fourth sheet that includes a
cathode material that includes lithium and a LiPON barrier/electrolyte
layer covering the cathode material, sandwiching a polymer electrolyte
material between the LiPON barrier/electrolyte layer covering the anode
material of the third sheet and the LiPON barrier/electrolyte layer
covering the cathode material of the fourth sheet, and sandwiching a
polymer electrolyte material between the LiPON barrier/electrolyte layer
covering the anode material of the first sheet and the LiPON
barrier/electrolyte layer covering the cathode material of the fourth
sheet.
In some embodiments of the method, the anode is deposited as a layer on
a copper anode current-collector contact layer through a LiPON layer.
In some embodiments of the method, the deposition of a lithium anode is
done by electroplating in a propylene carbonate/LiPF6 electrolyte
solution.
In some embodiments of the method, the first sheet includes a cathode
material on a face opposite the anode material and a LiPON
barrier/electrolyte layer covering the cathode material, and the second
sheet includes an anode material that includes lithium on a face opposite
the cathode material and a LiPON barrier/electrolyte layer covering the
anode material, wherein the method further includes providing a third
sheet that includes an anode material that includes lithium and a LiPON
barrier/electrolyte layer covering the anode material on a first face,
and an anode material that includes lithium and a LiPON
barrier/electrolyte layer covering the anode material on a second face
opposite the first face, and sandwiching a polymer electrolyte material
between the UPON barrier/electrolyte layer covering the anode material
of the first sheet and the LiPON barrier/electrolyte layer covering the
cathode material of the third sheet.
Some embodiments of the invention include an apparatus that includes a
first sheet that includes an anode material that includes lithium and a
LiPON barrier/electrolyte layer covering the anode material on a first
face of the first sheet, a second sheet that includes a cathode material
that includes lithium and a LiPON barrier/electrolyte layer covering the
cathode material on a second face of the second sheet, and means for
passing ions between the LiPON layer on the first face of the first sheet
and the LiPON layer on the second face of the second sheet to form a first
battery cell.
In some embodiments, the first sheet includes a LiPON layer on a second
face of the first sheet, and the apparatus further includes a third sheet
that includes an anode material that includes lithium and a LiPON
barrier/electrolyte layer covering the anode material on a first face of
the third sheet, a fourth sheet that includes a cathode material that
includes lithium and a LiPON barrier/electrolyte layer covering the
cathode material on a second face of the fourth sheet and a cathode
material that includes lithium and a LiPON barrier/electrolyte layer
covering the cathode material on a first face of the fourth sheet, means
for passing ions between the LiPON layer on the first face of the third
sheet and the LiPON layer on the second face of the fourth sheet to form
a second battery cell, and means for passing ions between the LiPON layer
on the second face of the first sheet and the LiPON layer on the first
face of the fourth sheet to form a third battery cell.
In some embodiments, the first sheet includes a copper anode
current-collector layer, and the anode material includes lithium
deposited as a lithium-metal layer on the copper anode current-collector
layer through the LiPON layer of the first sheet.
In some embodiments, a periphery of the lithium-metal layer is defined
by a mask, and the deposition of a lithium anode is done by electroplating
in a liquid propylene carbonate/LiPF6 electrolyte solution.
In some embodiments, the first sheet includes a cathode material on a
second face opposite the anode material on the first face and a LiPON
barrier/electrolyte layer covering the cathode material of the first
sheet, and the apparatus further includes a third sheet having an anode
material that includes lithium and a LiPON barrier/electrolyte layer
covering the anode material on a first face of the third sheet, and means
for passing ions between the LiPON layer on the second face of the first
sheet and the LiPON layer on the first face of the third sheet to form
a series-connected pair of battery cells.
Some embodiments of the invention include an apparatus that includes a
deposition station that deposits a hard electrolyte layer on a negative
electrode component, a deposition station that deposits a hard
electrolyte layer on a positive electrode component, and a lamination
station that laminates the hard electrolyte layer on the negative
electrode component to the hard electrolyte layer on the positive
electrode component with a soft electrolyte layer therebetween to form
a composite electrolyte structure.
Some embodiments further include a deposition station that deposits a soft
electrolyte layer on the hard electrolyte layer on the negative electrode
component. In some embodiments, the soft electrolyte layer includes a
polyphosphazene.
Some embodiments further include a deposition station that deposits a soft
electrolyte layer on the hard electrolyte layer on the negative electrode
component, and a deposition station that deposits a soft electrolyte layer
on the hard electrolyte layer on the positive electrode component.
In some embodiments, the deposition station that deposits the hard
electrolyte layer on the positive electrode deposits a material that
includes LiPON, the deposition station that deposits the hard electrolyte
layer on the negative electrode component deposits a material that
includes LiPON, and the deposition station that deposits the soft
electrolyte layer deposited on the hard electrolyte layer on the positive
electrode component and the deposition station that deposits the soft
electrolyte layer on the hard electrolyte layer on the negative electrode
deposits a material that includes a polyphosphazene and a lithium salt.
In some embodiments, the soft electrolyte layer includes MEEP.
In some embodiments, the deposition station that deposits the hard
electrolyte layer on the positive electrode deposits a material that
includes LiPON and the deposition station that deposits the hard
electrolyte layer on the negative electrode deposits a material that
includes LIPON.
Some embodiments further include a deposition station that deposits a
LiCoO2 layer on the positive electrode before the hard electrolyte layer
is deposited on the positive electrode component.
Some embodiments further include an electroplating station that plates
a lithium metal layer on the negative electrode through the hard
electrolyte layer after the hard electrolyte layer is deposited on the
negative electrode component.
Some embodiments further include a patterning station that deposits a
photoresist layer and patterns a mask that defines an area on the negative
electrode component to which a lithium metal layer can be formed.
Some embodiments of the invention include a method that includes providing
a positive electrode component, providing a negative electrode component,
depositing a hard electrolyte layer on the negative electrode component,
depositing a hard electrolyte layer on a positive electrode component,
and laminating the hard electrolyte layer on the negative electrode to
the hard electrolyte layer on the positive electrode with a soft
electrolyte layer therebetween to form a composite electrolyte structure.
In some embodiments of the method, the depositing of the hard electrolyte
layer on the positive electrode component includes sputtering a LiPON
layer, and the depositing of the hard electrolyte layer on the negative
electrode component includes sputtering a LiPON layer.
In some embodiments of the method, the soft electrolyte layer includes
a polyphosphazene and a lithium salt.
Some embodiments further include depositing a soft electrolyte layer on
the hard electrolyte layer on the negative electrode component, and
depositing a soft electrolyte layer on the hard electrolyte layer on a
positive electrode component, and wherein the laminating presses the soft
electrolyte layer on the hard electrolyte layer on the negative electrode
component against the soft electrolyte layer on the hard electrolyte layer
on the positive electrode component.
In some embodiments, the depositing of the soft electrolyte layer on the
hard electrolyte layer on the negative electrode component includes
doctor blading.
In some embodiments, the depositing of the soft electrolyte layer on the
hard electrolyte layer on the negative electrode component includes
spraying soft electrolyte material in a liquid form.
In some embodiments, the depositing of the soft electrolyte layer on the
hard electrolyte layer on the positive electrode component includes spin
coating soft electrolyte material in a liquid form.
Some embodiments of the invention include an apparatus that includes a
source of a positive electrode component, a source of a negative electrode
component, means for depositing a hard electrolyte layer on the negative
electrode component, means for depositing a hard electrolyte layer on a
positive electrode component, and means for laminating the hard
electrolyte layer on the negative electrode to the hard electrolyte layer
on the positive electrode with a soft electrolyte layer therebetween to
form a composite electrolyte structure.
Some embodiments further include means for depositing a soft electrolyte
layer on the hard electrolyte layer on the negative electrode component,
and means for depositing a soft electrolyte layer on the hard electrolyte
layer on a positive electrode component, and wherein the means for
laminating presses the soft electrolyte layer on the hard electrolyte
layer on the negative electrode component against the soft electrolyte
layer on the hard electrolyte layer on the positive electrode component.
In some embodiments, the hard electrolyte layer deposited on the positive
electrode component includes LiPON and the hard electrolyte layer
deposited on the negative electrode component includes LiPON.
In some embodiments, the soft electrolyte layers include a
polyphosphazene and a lithium salt.
In some embodiments, the soft electrolyte layers include MEEP.
Some embodiments of the invention include an apparatus that includes a
battery cell having an anode, a cathode, and an electrolyte structure,
wherein the anode includes an anode material that, when the battery cell
is charged, includes lithium and a LiPON barrier/electroly
2 7,931,989 Thin-film batteries with soft and hard electrolyte layers and
method
United States Patent
7,931,989
Klaassen
April 26, 2011
Abstract
A method and apparatus for making thin-film batteries having composite
multi-layered electrolytes with soft electrolyte between hard
electrolyte covering the negative and/or positive electrode, and the
resulting batteries. In some embodiments, foil-core cathode sheets each
having a cathode material (e.g., LiCoO.sub.2) covered by a hard
electrolyte on both sides, and foil-core anode sheets having an anode
material (e.g., lithium metal) covered by a hard electrolyte on both sides,
are laminated using a soft (e.g., polymer gel) electrolyte sandwiched
between alternating cathode and anode sheets. A hard glass-like
electrolyte layer obtains a smooth hard positive-electrode lithium-metal
layer upon charging, but when very thin, have randomly spaced
pinholes/defects. When the hard layers are formed on both the positive
and negative electrodes, one electrode's dendrite-short-causing defects
on are not aligned with the other electrode's defects. The soft
electrolyte layer both conducts ions across the gap between hard
electrolyte layers and fills pinholes.
Inventors: Klaassen; Jody J. (Minneapolis, MN)
Assignee: CYMBET Corporation (Elk River, MN)
Appl. No.: 11/458,091
Filed:
July 17, 2006
Related U.S. Patent Documents
Application Number Filing Date Patent Number Issue Date<TD< TD>
60699895
Jul., 2005
<TD< TD>
Current U.S. Class:
429/300 ; 429/126; 429/304
Current International Class:
Field of Search:
H01M 6/14
(20060101)
429/47-347 29/623.1-625 427/1-601
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WO 2007/011900
Jan., 2007
WO
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Primary Examiner: Yuan; Dah-Wei D
Assistant Examiner: Best; Zachary
Attorney, Agent or Firm: Kagan Binder, PLLC
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This invention claims benefit of U.S. Provisional Patent Application
60/699,895 filed Jul. 15, 2005, which is hereby incorporated by reference
in its entirety. This is also related to U.S. patent application Ser. No.
10/895,445 entitled "LITHIUM/AIR BATTERIES WITH LiPON AS SEPARATOR AND
PROTECTIVE BARRIER AND METHOD" filed Oct. 16, 2003 by J. Klaassen, the
inventor of the present application, and to U.S. patent application Ser.
No. 11/031,217 entitled "LAYERED BARRIER STRUCTURE HAVING ONE OR MORE
DEFINABLE LAYERS AND METHOD" filed Jan. 6, 2005, U.S. patent application
Ser. No. 11/458,093 entitled "THIN-FILM BATTERIES WITH POLYMER AND LiPON
ELECTROLYTE LAYERS AND METHOD" and U.S. patent application Ser. No.
11/458,097 entitled "APPARATUS AND METHOD FOR MAKING THIN-FILM BATTERIES
WITH SOFT AND HARD ELECTROLYTE LAYERS", filed on even date herewith, which
are all incorporated herein in their entirety by reference.
Claims
What is claimed is:
1. A method of forming a battery cell having a composite electrolyte
structure comprising: a) providing a positive electrode component; b)
providing a negative electrode component; c) depositing a first
electrolyte layer having randomly spaced defects therein on the negative
electrode component; d) depositing a second electrolyte layer having
randomly spaced defects therein on a positive electrode component; e)
providing a third electrolyte material that comprises a polymer or a gel
that is soft compared to the first and second electrolyte layers; f)
laminating the first electrolyte layer on the negative electrode to the
second electrolyte layer on the positive electrode using the third soft
electrolyte material to at least partially fill and fix the defects in
at least one of the first and second electrolyte layers to form the
composite electrolyte structure of the battery cell.
2. The method of claim 1, further comprising laminating two or more battery
cells together to form a laminated battery device.
3. The method of claim 1, wherein the laminated battery device comprises
a stack of two-sided anode current collectors and two-sided cathode
current collectors that are connected in parallel.
4. The method of claim 1, wherein the laminated battery device comprises
a stack of two-sided anode current collectors and two-sided cathode
current collectors that are connected in series.
5. The method of claim 1, wherein the third electrolyte layer is an
adhesive that provides a structural connection between the first and
second electrolyte layers.
6. The method of claim 1, wherein the positive electrode component
comprises a current collector onto which is deposited a cathode material.
7. The method of claim 1, wherein the negative electrode component
comprises a current collector, and wherein a layer of lithium is formed
as an active portion of the negative electrode component after assembly
of the battery cell.
8. The method of claim 1, wherein the first and second electrolyte layers
are LiPON.
9. The method of claim 1, wherein the third electrolyte layer is sticky.
10. The method of claim 8, wherein the third electrolyte layer comprises
polyvinylidene difluoride, propylene carbonate, and a lithium salt.
11. The method of claim 8, wherein the third electrolyte layer comprises
MEEP.
12. The method of claim 1, wherein the cathode electrode component
includes LiCoO.sub.2 that is deposited on a positive electrode
current-collector material, and the second electrolyte layer on the
positive electrode component is a layer of LiPON that is deposited on the
LiCoO.sub.2.
13. The method of claim 1, wherein the negative electrode component
includes a negative-electrode current collector made of a metal that does
not readily alloy with lithium during a plating operation, and lithium
metal is plated onto the negative-electrode current collector through the
first electrolyte layer on the negative electrode component.
14. The method of claim 1, wherein the third electrolyte layer comprises
a polyphosphazene and a lithium salt.
Description
FIELD OF THE INVENTION
This invention relates to solid-state energy-storage devices, and more
specifically to a method and apparatus for making thin-film (e.g., lithium)
battery devices with a soft (e.g., polymer) electrolyte layer, and one
or more hard layers (e.g., LiPON) as electrolyte layer(s) and/or
protective barrier(s), and the resulting cell(s) and/or battery(s).
BACKGROUND OF THE INVENTION
Electronics have been incorporated into many portable devices such as
computers, mobile phones, tracking systems, scanners, and the like. One
drawback to portable devices is the need to include the power supply with
the device. Portable devices typically use batteries as power supplies.
Batteries must have sufficient capacity to power the device for at least
the length of time the device is in use. Sufficient battery capacity can
result in a power supply that is quite heavy and/or large compared to the
rest of the device. Accordingly, smaller and lighter batteries (i.e.,
power supplies) with sufficient energy storage are desired. Other energy
storage devices, such as supercapacitors, and energy conversion devices,
such as photovoltaics and fuel cells, are alternatives to batteries for
use as power supplies in portable electronics and non-portable electrical
applications.
Another drawback of conventional batteries is the fact that some are
fabricated from potentially toxic materials that may leak and be subject
to governmental regulation. Accordingly, it is desired to provide an
electrical power source that is safe, solid-state and rechargeable over
many charge/discharge life cycles.
One type of an energy-storage device is a solid-state, thin-film battery.
Examples of thin-film batteries are described in U.S. Pat. Nos. 5,314,765;
5,338,625; 5,445,906; 5,512,147; 5,561,004; 5,567,210; 5,569,520;
5,597,660; 5,612,152; 5,654,084; and 5,705,293, each of which is herein
incorporated by reference. U.S. Pat. No. 5,338,625 describes a thin-film
battery, especially a thin-film microbattery, and a method for making same
having application as a backup or first integrated power source for
electronic devices. U.S. Pat. No. 5,445,906 describes a method and system
for manufacturing a thin-film battery structure formed with the method
that utilizes a plurality of deposition stations at which thin battery
component films are built up in sequence upon a web-like substrate as the
substrate is automatically moved through the stations.
U.S. Pat. No. 6,805,998 entitled "METHOD AND APPARATUS FOR INTEGRATED
BATTERY DEVICES" (which is incorporated herein by reference) issued Oct.
19, 2004, by Mark L. Jenson and Jody J. Klaassen (the inventor of the
present application), and is assigned to the assignee of the present
invention, described a high-speed low-temperature method for depositing
thin-film lithium batteries onto a polymer web moving through a series
of deposition stations.
K. M. Abraham and Z. Jiang, (as described in U.S. Pat. No. 5,510,209, which
is incorporated herein by reference) demonstrated a cell with a
non-aqueous polymer separator consisting of a film of polyacrylonitrile
swollen with a propylene carbonate/ethylene carbonate/LiPF.sub.6
electrolyte solution. This organic electrolyte membrane was sandwiched
between a lithium metal foil anode and a carbon composite cathode to form
the lithium-air cell. The utilization of the organic electrolyte allowed
good performance of the cell in an oxygen or dry air atmosphere.
As used herein, the anode of the battery is the positive electrode (which
is the anode during battery discharge) and the cathode of the battery is
the negative electrode (which is the cathode during battery discharge).
(During a charge operation, the positive electrode is the cathode and the
negative electrode is the anode, but the anode-cathode terminology herein
reflects the discharge portion of the cycle.)
U.S. Pat. No. 6,605,237 entitled "Polyphosphazenes as gel polymer
electrolytes" (which is incorporated herein by reference), issued to
Allcock, et al. on Aug. 12, 2003, and describes co-substituted linear
polyphosphazene polymers that could be useful in gel polymer electrolytes,
and which have an ion conductivity at room temperature of at least about
10.sup.-5 S/cm and comprising (i) a polyphosphazene having controlled
ratios of side chains that promote ionic conductivity and hydrophobic,
non-conductive side chains that promote mechanical stability, (ii) a
small molecule additive, such as propylene carbonate, that influences the
ionic conductivity and physical properties of the gel polymer
electrolytes, and (iii) a metal salt, such as lithium
trifluoromethanesulfonate, that influences the ionic conductivity of the
gel polymer electrolytes, and methods of preparing the polyphosphazene
polymers and the gel polymer electrolytes. Allcock et al. discuss a system
that has been studied extensively for solid-polymer electrolyte (SPE)
applications, which is one that is based on poly(organophosphazenes).
This class of polymers has yielded excellent candidates for use in SPEs
due to the inherent flexibility of the phosphorus-nitrogen backbone and
the ease of side group modification via macromolecular substitution-type
syntheses. The first poly(organophosphazene) to be used in a phosphazene
SPE (solid polymer electrolyte) was poly[bis(2-(2'-methoxyethoxy
ethoxy)phosphazene] (hereinafter, MEEP). This polymer was developed in
1983 by Shriver, Allcock and their coworkers (Blonsky, P. M., et al,
Journal of the American Chemical Society, 106, 6854 (1983)) and is
illustrated in U.S. Pat. No. 6,605,237.
Also, the following U.S. Pat. Nos. 7,052,805 (Polymer electrolyte having
acidic, basic and elastomeric subunits, published/issued on May 30, 2006);
6,783,897 (Crosslinking agent and crosslinkable solid polymer
electrolyte using the same, Aug. 31, 2004); 6,727,024 (Polyalkylene oxide
polymer composition for solid polymer electrolytes, Apr. 27, 2004);
6,392,008 (Polyphosphazene polymers, May 21, 2002); 6,369,159
(Antistatic plastic materials containing epihalohydrin polymers, Apr. 9,
2002); 6,214,251 (Polymer electrolyte composition, Apr. 10, 2001);
5,998,559 (Single-ion conducting solid polymer electrolytes, and
conductive compositions and batteries made therefrom; Dec. 7, 1999);
5,874,184 (Solid polymer electrolyte, battery and solid-state electric
double layer capacitor using the same as well as processes for the
manufacture thereof, Feb. 23, 1999); 5,698,664 (Synthesis of
polyphosphazenes with controlled molecular weight and polydispersity,
Dec. 16, 1997); 5,665,490 (Solid polymer electrolyte, battery and
solid-state electric double layer capacitor using the same as well as
processes for the manufacture thereof, Sep. 9, 1997); 5,633,098
(Batteries containing single-ion conducting solid polymer electrolytes,
May 27, 1997); 5,597,661 (Solid polymer electrolyte, battery and
solid-state electric double layer capacitor using the same as well as
processes for the manufacture thereof, Jan. 28, 1997); 5,567,783
(Polyphosphazenes bearing crown ether and related pod and side groups as
solid solvents for ionic conduction, Oct. 22, 1996); 5,562,909
(Phosphazene polyelectrolytes as immunoadjuvants, Oct. 8, 1996);
5,548,060 (Sulfonation of polyphosphazenes, Aug. 20, 1996); 5,414,025
(Method of crosslinking of solid state battery electrolytes by
ultraviolet radiation, May 9, 1995); 5,376,478 (Lithium secondary battery
of vanadium pentoxide and polyphosphazenes, Dec. 27, 1994); 5,219,679
(Solid electrolytes, Jun. 15, 1993); 5,110,694 (Secondary Li battery
incorporating 12-Crown-4 ether, May 5, 1992); 5,102,751 (Plasticizers
useful for enhancing ionic conductivity of solid polymer electrolytes,
Apr. 7, 1992); 5,061,581 (Novel solid polymer electrolytes, Oct. 29, 1991);
4,656,246 (Polyetheroxy-substituted polyphosphazene purification, Apr.
7, 1987); and 4,523,009, (Polyphosphazene compounds and method of
preparation, Jun. 11, 1985), which are all incorporated herein by
reference. Each discuss polyphosphazene polymers and/or other polymer
electrolytes and/or lithium salts and combinations thereof
U.S. patent application Ser. No. 10/895,445 entitled "LITHIUM/AIR
BATTERIES WITH LiPON AS SEPARATOR AND PROTECTIVE BARRIER AND METHOD" by
the inventor of the present application (which is incorporated herein by
reference) describes a method for making lithium batteries including
depositing LiPON on a conductive substrate (e.g., a metal such as copper
or aluminum) by depositing a chromium adhesion layer on an electrically
insulating layer of silicon oxide by vacuum sputter deposition of 50 nm
of chromium followed by 500 nm of copper. In some embodiments, a thin film
of LiPON (Lithium Phosphorous OxyNitride) is then formed by low-pressure
(<10 mtorr) sputter deposition of lithium orthophosphate
(Li.sub.3PO.sub.4) in nitrogen. In some embodiments of the Li-air battery
cells, LiPON was deposited over the copper anode current-collector
contact to a thickness of 2.5 microns, and a layer of lithium metal was
formed onto the copper anode current-collector contact by electroplating
through the LiPON layer in a propylene carbonate/LiPF.sub.6 electrolyte
solution. In some embodiments, the air cathode was a
carbon-powder/polyfluoroacrylate-binder coating (Novec-1700) saturated
with a propylene carbonate/LiPF.sub.6 organic electrolyte solution. In
other embodiments, a cathode-current-collector contact layer having
carbon granules is deposited, such that atmospheric oxygen could operate
as the cathode reactant. This configuration requires providing air access
to substantially the entire cathode surface, limiting the ability to
densely stack layers for higher electrical capacity (i.e., amp-hours).
There is a need for rechargeable lithium-based batteries having improved
protection against dendrite formation and with improved density,
electrical capacity, rechargeability, and reliability, and smaller
volume and lowered cost.
BRIEF SUMMARY OF THE INVENTION
In some embodiments, the present invention includes a battery having an
electrolyte structure that combines a plurality of layers of different
electrolytes (e.g., hard-soft-hard). In some embodiments, a thin (0.1 to
1.0 micron) LiPON electrolyte layer serves as a hard coating on the
negative electrode preventing the formation of lithium dendrites
(especially when paired with a corresponding LiPON electrolyte layer
coating on the positive electrode) and/or providing an even (smooth), hard
layer of lithium metal on, or as part of, the negative electrode when the
battery is charged. In some embodiments, a thin (0.1 to 1.0 micron) LiPON
electrolyte on only one electrode (e.g., the negative electrode) may not
prevent the formation of lithium dendrites over the long term (e.g., many
thousands of discharge-recharge cycles), since the lithium growing
through a pinhole may only need to grow about 3 microns or less across
the electrolyte to short the battery (i.e., providing a metal electrical
conduction path directly from anode to cathode). When LiPON is also used
as a coating at the positive electrode (e.g., an electrode that includes
LiCoO.sub.2) the random locations of the pinholes will not line up (e.g.,
across the electrolyte from anode to cathode) so lithium would also need
to grow sideways in the electrolyte, which doubly ensures that lithium
plating at a defect site (which would typically form a dendrite) will not
short the battery. In some embodiments, a soft electrolyte layer bridges
the gap between the hard electrolyte layer on the negative electrode and
the hard electrolyte layer on the positive electrode. At both electrodes,
the LiPON layer also provides an improvement in environmental resistance
to water vapor and oxygen, especially during manufacture before the
battery is completed and otherwise sealed. In some embodiments, the soft
electrolyte includes a solid polymer electrolyte (SPE) layer that is
located between and contacts with the LiPON layer on the positive
electrode and the LiPON layer on the negative electrode. In some
embodiments, the electrolyte structure includes a polymer electrolyte
such as PEO-LiX (poly-ethylene oxide lithium-X, where LiX=a metal salt,
such as LiPF6, LiBF.sub.4, LiCF.sub.3SO.sub.4, CF.sub.3SO.sub.3Li
(lithium trifluoromethanesulfonate, also called triflate), lithium
bisperfluoroethanesulfonimide,
lithium(Bis)Trifluoromethanesulfonimide, and/or the like, for example).
In some embodiments, the electrolyte structure includes a polymer
electrolyte such as polyPN-LiX (Polyphosphazene with lithium-X, where
LiX=LiPF.sub.6, LiBF.sub.4, LiCF.sub.3SO.sub.4, and/or the like, for
example). In some embodiments, a small-molecule additive, such as
propylene carbonate, that influences the ionic conductivity and physical
properties of the polymer electrolytes is added to form a gel electrolyte
that better fills defects and acts as an adhesive.
The present invention provides both a method and an apparatus for making
thin-film batteries having composite (e.g., multi-layered) electrolytes
with a soft electrolyte layer between hard electrolyte layers covering
the negative and/or positive electrodes, and the resulting batteries. In
some embodiments, metal-core cathode sheets each having a cathode
material (e.g., LiCoO2) deposited on a metal foil, screen, or mesh (e.g.,
copper, nickel, or stainless steel) or a metal-covered insulator (e.g.,
a sputtered metal film on a polymer film, a SiO2-covered silicon wafer,
or an alumina or sapphire substrate) and is covered by a hard electrolyte
(some embodiments form such electrodes on both sides of the substrate),
and foil-core anode sheets having a anode material (e.g., lithium metal)
deposited on a metal foil (e.g., copper, nickel, or stainless steel) or
a metal-covered insulator (e.g., a sputtered metal film on a polymer film,
a SiO2-covered silicon wafer, or an alumina or sapphire substrate) and
is also covered by a hard electrolyte (some embodiments form such
electrodes on both sides of the substrate), and such sheets are laminated
using a soft (e.g., polymer gel) electrolyte sandwiched between
alternating cathode and anode sheets. In some embodiments, a hard
glass-like electrolyte layer obtains a smooth hard positive-electrode
lithium-metal layer upon charging, but when such a layer is made very thin,
will tend to have randomly spaced pinholes/defects. When the hard layers
are formed on both the positive and negative electrodes, one electrode's
dendrite-short-causing defects on are not aligned with the other
electrode's defects. The soft electrolyte layer conducts ions across the
gap between hard electrolyte layers and/or fills pinholes, thin spots,
and other defects in the hard electrolyte layers.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a schematic cross-section view of a lithium cell 100 of some
embodiments of the invention.
FIG. 1B is a schematic cross-section view of a lithium cell 101 of some
embodiments of the invention.
FIG. 1C is a schematic cross-section view of a lithium cell 102 of some
embodiments of the invention.
FIG. 2 is a schematic cross-section view of a lithium-battery
manufacturing process 200 of some embodiments of the invention.
FIG. 3 is a schematic cross-section view of a parallel-connected lithium
battery 300 of some embodiments of the invention.
FIG. 4 is a schematic cross-section view of a series-connected lithium
battery 400 of some embodiments of the invention.
FIG. 5A is a schematic cross-section view of a parallel-connected
screen-cathode current-collector contact lithium-battery 500 of some
embodiments of the invention.
FIG. 5B is a schematic cross-section view of a series-connected
screen-cathode-current-collector contact lithium-battery 501 of some
embodiments of the invention.
FIG. 6A is a perspective view of an electrode 600 having a
hard-electrolyte-covered current collector with a plating mask 119.
FIG. 6B is a perspective view of another electrode 601 having a
hard-electrolyte-covered current collector with a plating mask 119.
FIG. 6C is a perspective view of a plating system 610.
FIGS. 7A, 7B, 7C, 7D, 7E, and 7F are schematic cross-sectional views of
the fabrication of an atomic level matrix of copper and copper oxides as
cathodes on a substrate of some embodiments of the invention.
FIGS. 8A, 8B, 8C, 8D, and 8E are schematic cross-sectional views of the
fabrication of an atomic level matrix of copper and copper oxides as
cathodes on a copper foil substrate of some embodiments of the invention.
FIG. 9 is a schematic cross-section view of a parallel-connected
foil-cathode-current-collector contact lithium battery 900 of some
embodiments of the invention.
FIG. 10A is a schematic cross-section view of an encapsulated
surface-mount micro-battery 1000 of some embodiments of the invention.
FIG. 10B is a perspective view of an encapsulated surface-mount
micro-battery 1000 of some embodiments of the invention.
FIG. 11 is a flow chart of a method 1100 for making a battery cell according
to some embodiments of the invention.
FIG. 12 is a flow chart of a method 1200 for making a stacked battery
according to some embodiments of the invention.
FIG. 13 is an exploded perspective view of an embodiment of a device as
part of a system.
FIG. 14 is an exploded perspective view of another embodiment of a device
as part of a portable system.
DETAILED DESCRIPTION OF THE INVENTION
Although the following detailed description contains many specifics for
the purpose of illustration, a person of ordinary skill in the art will
appreciate that many variations and alterations to the following details
are within the scope of the invention. Accordingly, the following
preferred embodiments of the invention are set forth without any loss of
generality to, and without imposing limitations upon the claimed
invention.
In the following detailed description of the preferred embodiments,
reference is made to the accompanying drawings that form a part hereof,
and in which are shown by way of illustration specific embodiments in which
the invention may be practiced. It is understood that other embodiments
may be utilized and structural changes may be made without departing from
the scope of the present invention.
The leading digit(s) of reference numbers appearing in the Figures
generally correspond to the Figure number in which that component is first
introduced, such that the same reference number is used throughout to
refer to an identical component, which appears in multiple Figures.
Signals (such as, for example, fluid pressures, fluid flows, or electrical
signals that represent such pressures or flows), pipes, tubing or conduits
that carry the fluids, wires or other conductors that carry the electrical
signals, and connections may be referred to by the same reference number
or label, and the actual meaning will be clear from its use in the context
of the description.
Terminology
In this description, the term metal applies both to substantially pure
single metallic elements and to alloys or combinations of two or more
elements, at least one of which is a metallic element.
The term substrate or core generally refers to the physical structure that
is the basic work piece that is transformed by various process operations
into the desired microelectronic configuration. In some embodiments,
substrates include conducting material (such as copper, stainless steel,
aluminum and the like), insulating material (such as sapphire, ceramic,
or plastic/polymer insulators and the like), semiconducting materials
(such as silicon), non-semiconducting, or combinations of semiconducting
and non-semiconducting materials. In some other embodiments, substrates
include layered structures, such as a core sheet or piece of material (such
as iron-nickel alloy and the like) chosen for its coefficient of thermal
expansion (CTE) that more closely matches the CTE of an adjacent structure
such as a silicon processor chip. In some such embodiments, such a
substrate core is laminated to a sheet of material chosen for electrical
and/or thermal conductivity (such as a copper, aluminum alloy and the
like), which in turn is covered with a layer of plastic chosen for
electrical insulation, stability, and embossing characteristics. An
electrolyte is a material that conducts electricity by allowing movement
of ions (e.g., lithium ions having a positive charge) while being
non-conductive or highly resistive to electron conduction. An electrical
cell or battery is a device having an anode and a cathode that are separated
by an electrolyte. A dielectric is a material that is non-conducting to
electricity, such as, for example, plastic, ceramic, or glass. In some
embodiments, a material such as LiPON can act as an electrolyte when a
source and sink for lithium are adjacent the LiPON layer, and can also
act as a dielectric when placed between two metal layers such as copper
or aluminum, which do not form ions that can pass through the LiPON. In
some embodiments, devices include an insulating plastic/polymer layer (a
dielectric) having wiring traces that carry signals and electrical power
horizontally, and vias that carry signals and electrical power vertically
between layers of traces.
In some embodiments, an anode portion of a thin-film solid-state battery
is made (as described in U.S. patent application Ser. No. 10/895,445
discussed above) using a method that includes depositing LiPON on a
conductive substrate (e.g., a metal such as copper or aluminum) that is
formed by depositing a chromium adhesion layer on an electrically
insulating layer of silicon oxide (or on a polymer sheet) using
vacuum-sputter deposition of 50 nm of chromium followed by 500 nm of copper.
In some embodiments, a thin film of LiPON (Lithium Phosphorous OxyNitride)
is then formed by low-pressure (<10 mtorr) sputter deposition of lithium
orthophosphate (Li.sub.3PO.sub.4) in nitrogen, or by sputtering from a
LiPON source. In some embodiments LiPON is deposited over the copper anode
current-collector contact to a thickness of between 0.1 microns and 2.5
microns. In some embodiments, a layer of lithium metal is formed onto the
copper anode current-collector contact by electroplating through the
LiPON layer (which was earlier deposited on the copper anode
current-collector contact) in a propylene carbonate/LiPF.sub.6 organic
electrolyte solution. The LiPON acts as a protective layer during
fabrication of the battery, and in the assembled battery, it operates as
one layer of a multi-layer electrolyte. (In other embodiments, the layer
of lithium metal of the anode is formed by an initial charging operation
after the battery is assembled.) In some embodiments, a cathode portion
of the thin-film solid-state battery is made sputtering LiCoO.sub.2 onto
a first of metal foil from a LiCoO.sub.2 source, over which is deposited
a LiPON layer, which in the assembled battery, operates as another layer
of the multi-layer electrolyte. In some embodiments, a solid or gel
polymer electrolyte is used as a structural connection or adhesive between
the two LiPON electrolyte layers, as well as forming an ion-conductive
path between the positive and negative electrodes of the battery.
It is desirable, in some embodiments, to form a very thin electrolyte.
If a single very thin layer of LiPON is used, it tends to have defects
(e.g., thin spots or pinholes) and lithium ions will preferentially travel
through these paths of least resistance and plate to spike-shaped
lithium-metal dendrites that short out the battery. If a single very thin
solid or gel polymer electrolyte layer is used, any surface irregularities
(e.g., bumps or ridges in the anode or cathode material) will tend to
connect through the electrolyte and short the battery. By having two
independently formed very thin LiPON (hard) electrolyte component layers,
one formed on the battery's anode and another formed on the battery's
cathode, any such thin spots or pinholes in one layer will not line up
with a thin spot or pinhole in the other layer. The third electrolyte layer
(e.g., a soft polymer electrolyte that conducts lithium ions between the
two LiPON layers) made of a solid and/or gel polymer electrolyte material
does not get shorted out by bumps or other irregularities in either
electrode since those irregularities will tend to be coated with LiPON
and/or the corresponding spot on the other side will be coated with LiPON.
Accordingly, one or more (even all) of the plurality of layers can be made
very thin without the danger of having an initial short (from a polymer
electrolyte that is too thin allowing the anode and cathode to touch) or
a later-developed short (from a pinhole in a LiPON electrolyte layer that
allows formation of a lithium-metal dendrite after one or more
charge/discharge cycles). Further, the dense, hard, glass-like LiPON
layer causes the lithium ions that pass through it to form a lithium-metal
layer that is dense and smooth. In other embodiments, one or more other
hard and/or glass-like electrolyte layers are used instead of one or more
of the LiPON layers.
U.S. Pat. No. 6,605,237 entitled "Polyphosphazenes as gel polymer
electrolytes" discusses MEEP (poly[bis(2-(2'-methoxyethoxy
ethoxy)phosphazene]) and other polymers, which are used in some
embodiments of the present invention as structural connector and polymer
electrolyte sublayer between two LiPON sublayers. The polyphosphazene
(herein called polyPN) used as the connective layer is soft and sticky.
Its adhesive properties are what allow the electrode to be and to remain
joined. Its softness allows for defect correction and/or for defects to
not cause poor battery performance and reliability. In other embodiments,
other soft or gel-like ion-conducting polymers are used.
U.S. Pat. Nos. 4,523,009, 5,510,209, 5,548,060, 5,562,909, 6,214,251,
6,392,008 6,605,237, and 6,783,897 (which are all incorporated herein by
reference) each discuss polyphosphazene polymers and/or other polymer
electrolytes and/or various lithium salts and compounds that can be used
as, or included in, one or more component layers of an electrolyte in some
embodiments of the present invention.
The term vertical is defined to mean substantially perpendicular to the
major surface of a substrate. Height or depth refers to a distance in a
direction perpendicular to the major surface of a substrate.
FIG. 1A is a schematic cross-section view of a lithium cell 100 of some
embodiments of the invention. In some embodiments, cell 100 includes a
first sheet 111 (a cathode or positive-electrode subassembly) having a
first metal foil 110 (which acts as a current collector) onto which is
deposited a film of cathode material 112, such as, for example,
LiCoO.sub.2, for example, by sputtering from a LiCoO.sub.2 target, and
over which is deposited a relatively hard LiPON layer 114 (which acts as
a hard-electrolyte current spreader). In some embodiments, cell 100
includes a second sheet 121 (an anode or negative-electrode subassembly)
having a second metal foil 120 (which acts as a current collector) onto
which is deposited a film of LiPON 124 (which acts as a hard-electrolyte
current spreader and as an environmental barrier for lithium that is later
plated through this layer), and a layer of lithium 122 (which forms the
active portion of the anode or negative-electrode) is plated through the
LiPON film 124 (either before or after the entire battery is assembled:
if the cathode contains sufficient lithium to start, then the anode
lithium layer is formed after assembly by the initial charging of the
battery, while if the cathode has little or no lithium to start with, then
the anode lithium layer is formed before assembly, e.g., by electroplating
in a liquid electrolyte or solution from an external sacrificial
lithium-metal electrode). In some embodiments, a sheet or layer of polymer
electrolyte 130 is sandwiched between the first sheet 111 and the second
sheet 121. In some embodiments, the layer of the polymer electrolyte is
deposited onto LiPON layer 114, LiPON layer 124, or a portion of the
polymer electrolyte is deposited onto both LiPON layer 114 and LiPON layer
124, and then the first sheet 111 and the second sheet 121 are pressed
together or otherwise assembled (in some embodiments, two or more of the
sheets are squeezed together between a pair of rollers).
In some embodiments, it is the hard-soft-hard combination of electrolyte
layers that provide a low-cost, high-quality, high-reliability, highly
rechargeable battery system. In some embodiments, the hard layers act as
protective barrier layers during manufacture and as current spreader
electrolytes that obtain a smooth hard layer of lithium on the anode upon
charging. In some embodiments, the hard layers are or include a glass or
glass-like electrolyte material (e.g., LiPON). When they are made very
thin (in order to increase cell conductivity and reduce cell resistance),
these hard layers tend to have randomly spaced pinholes, bumps, or other
defects (thicker layers can eliminate many such defects, but will have
decreased cell conductivity and increased cell resistance). When the hard
layers are formed on both the positive electrode and the corresponding
negative electrode, the pinholes and defects of the electrolyte covering
one electrode will tend not to be aligned with the pinholes and defects
of the electrolyte covering the other electrode. The soft electrolyte
layer both conducts ions across the gap between hard layers and tends to
fill the pinholes and defects of the hard electrolyte coverings. In some
embodiments, the soft electrolyte layer can be a solid or gel polymer
electrolyte (these also act as adhesives to hold the cells together and
as seals to reduce contamination of the cell from environmental factors
and to reduce leakage of the soft electrolyte layer), or can be a liquid
electrolyte, optionally infused in a structural element (such as a sponge,
screen, or ridges formed of a host solid-polymer (e.g., polyethylene,
polypropylene, fluoroethylene or the like) on one or more of the hard
electrolyte layers (e.g., by microembossing).
In some embodiments, the soft electrolyte layer includes a gel that
includes a polyvinylidene difluoride (PVdF), propylene carbonate, and a
lithium salt. PVdF is a polymer that does not conduct lithium ions, that
is, lithium salts will not dissolve in PVdF. However, PVdF can be swollen
with a liquid such as propylene carbonate in which a lithium salt has been
dissolved. The gel that results can be used as a soft electrolyte.
In some embodiments, the thickness of each of the hard electrolyte layers
is one micron or thinner, and the thickness of the soft electrolyte layer
is about three microns or thinner. The structure shown in FIG. 1A is also
represented in the following Table 1:
TABLE-US-00001 TABLE 1 Reference Function or Number Property Example
Materials . . . optionally, more battery layers stacked above . . . 110
cathode metal foil (e.g., one that does not current alloy with Li, such
as copper, collector nickel, stainless steel and the like), metal screen,
or metal film on polymer film or SiO.sub.2 layer on Si wafer, (can have
electrode formed on both sides for battery stack) 112 cathode LiCoO.sub.2
(sputtered or powder-pressed in material place), carbon powder, CuO
powder (any of the above can be infused with polyPN electrolyte material
to increase conductivity and lithium transport), or atomic matrix of
copper and copper oxides (which, in some embodiments, includes a tapered
composition Cu and O structure with more copper towards the top and more
oxygen towards the bottom, e.g., Cu metal gradually mixed to . . .
Cu.sub.4O . . . Cu.sub.2O . . . Cu.sup.+O.sup.-- . . . CuO) 114 hard LiPON
or other lithium-glass material electrolyte 130 soft polyPN with lithium
(e.g., LiPF.sub.6), or electrolyte other polymer (e.g., PEO,
polypropylene, etc.) electrolyte material 124 hard LiPON or other
lithium-glass material electrolyte 122 anode Lithium, (can be plated
through the material hard (e.g., LiPON) layer before or after assembly)
(could be zinc with suitable changes to electrolytes and cathode material)
110 anode metal foil (e.g., copper), metal screen, current or metal film
on polymer film or SiO.sub.2 collector layer on Si wafer, (can have
electrode formed on both sides for battery stack) . . . optionally, more
battery layers stacked below
FIG. 1B is a schematic cross-section view of a lithium cell 101 of some
embodiments of the invention. In some embodiments, cell 101, which is
assembled in an uncharged state, includes a first sheet 111 (a cathode
or positive-electrode subassembly) similar to that of FIG. 1A, except that
the hard electrolyte 114 extends laterally over first metal foil 110 well
beyond the lateral edges of the film of cathode material 112. In some
embodiments, the lateral extent of cathode material 112 (such as, for
example, LiCoO.sub.2, for example) is defined using photoresist and
lithographic processes similar to those used for semiconductor integrated
circuits (e.g., the cathode material is masked using photoresist, or a
hard material such as SiO.sub.2 covered by photoresist and etched and the
photoresist is removed so that the hard layer (e.g., SiO.sub.2) acts as
the mask, to define the lateral extent of cathode material 112 (e.g.,
LiCoO.sub.2), and the mask is then removed. The hard electrolyte layer
114 (e.g., LiPON) is deposited on the cathode material 112 as well as onto
substrate 110 around the sides of cathode material 112. This sideward
extension of the hard LiPON layer 114 acts as a seal to the sides of the
lithium in the cathode to protect it from environmental contaminants such
as oxygen or water vapor. In some embodiments, cell 101 includes a second
sheet 121 (an anode or negative-electrode subassembly similar to that of
FIG. 1A, except that no lithium is yet present) having a second metal foil
120 (which acts as a current collector) onto which is deposited a film
of LiPON 124 (which acts as a hard-electrolyte current spreader and as
an environmental barrier for lithium that is later plated through this
layer), and a mask layer 119 around all of the sides of what will be plated
lithium layer 122 (see FIG. 1C) that is later plated through the portions
of LiPON film 124 not covered by mask 119 (after the entire battery is
assembled). (In other embodiments, mask layer 119 is an electrical
insulator, such as SiO.sub.2, deposited directly on metal foil 120, and
photolithographically patterned to expose the metal substrate in the
center, and the hard electrolyte layer LiPON film 124 is deposited on top
of the mask layer). In some embodiments, the mask material 119 is
photoresist and/or an insulator such as SiO.sub.2 that have lateral
extents that are photolithographically defined. As above, in some
embodiments, a layer of soft polymer electrolyte 130 (either a solid
polymer electrolyte (SPE) or a gel or liquid polymer electrolyte) (such
as polyphosphazene having lithium salts such as LiPF.sub.6 to assist
lithium conductivity) is sandwiched between the first sheet 111 and the
second sheet 121.
FIG. 1C is a schematic cross-section view of a lithium cell 102 of some
embodiments of the invention. In some embodiments, the lithium metal layer
122 is plated before assembly (a combination of the methods described for
FIG. 6C and FIG. 2 below). In other embodiments, a battery 101 (such as
shown in FIG. 1B) is assembled before any lithium metal is in the anode
assembly 121, and is initially charged by plating lithium from the cathode
112 through electrolyte layers 114, 130, and 124 and onto the anode current
collector 120 to form lithium metal layer 122.
FIG. 2 is a schematic cross-section view of a lithium-battery
manufacturing process 200 of some embodiments of the invention. In some
embodiments, one or more double-sided anode sheets 121 are alternated with
one or more cathode sheets 111 (wherein an cathode material 112 is
deposited on both major faces of foil 110 inside of LiPON layer 114), with
a polymer layer 130 placed or form
3 7,931,985 Water soluble polymer binder for lithium ion battery
United States Patent
Muthu ,
7,931,985
et al.
April 26, 2011
Abstract
An electrode for a rechargeable lithium ion battery includes an
electro-active material, a (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer, and a conductive additive. A
battery using the inventive electrode is also disclosed.
Inventors: Muthu; Milburn Ebenezer Jacob (Breinigsville, PA), Mamari;
Monira (Allentown, PA), Crane; Chester (Bangor, PA)
Assignee: International Battery, Inc. (Allentown, PA)
Appl. No.: 12/941,100
Filed:
November 8, 2010
Current U.S.
Class:
Current
International
Class:
429/217 ; 429/212; 429/231.1; 429/231.95; 429/232
H01M 4/62
(20060101); H01M 4/58
(20060101)
Field of Search: 429/217,212,209,231.1,231.95,231.3,232,223,224,218.1
428/474.4,476.9,492,522
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Other References
Title: "Effect of pH on the Synthesis of LiCoO2 with Malonic Acid
and Its Charge/Discharge Behavior for a Lithium Secondary Battery"
Source: Bulletin of the Korean Chemical Society 2000, vol. 21, No.
11 pp. 1125-1132. cited by other.
Primary Examiner: Alejandro; Raymond
Attorney, Agent or Firm: Design IP
Claims
What is claimed is:
1. A battery comprising: a positive electrode mix comprising: a positive
electrode active material; and a water soluble binder comprising a
(polystyrenebutadiene rubber)-poly (acrylonitrile-co-acrylamide)
polymer; and a negative electrode mix comprising: a negative electrode
active material; and a water soluble binder comprising a
(polystyrenebutadiene rubber)-poly (acrylonitrile-co-acrylamide)
polymer; and an electrolyte.
2. The battery according to claim 1, wherein the positive electrode active
material comprises between about 80 and about 95 percent (by weight) of
the positive electrode mix.
3. The battery according to claim 2, wherein the conductive additive
material comprises between about 1 and about 20 percent (by weight) of
the positive electrode mix.
4. The battery according to claim 3, wherein the water soluble binder
comprises between about 1 and about 10 percent (by weight) of the positive
electrode mix.
5. The battery according to claim 1, wherein the negative electrode active
material comprises between about 80 and about 95 percent (by weight) of
the negative electrode mix.
6. The battery according to claim 5, wherein the conductive additive
material comprises between about 0 and about 20 percent (by weight) of
the negative electrode mix.
7. The battery according to claim 6, wherein the water soluble binder
comprises between about 1 and about 10 percent (by weight) of the negative
electrode mix.
8. The battery according to claim 1, wherein the water soluble binder is
provided in the absence of a thickening agent.
9. The battery according to claim 1, wherein the water soluble binder is
provided in the absence of a wetting agent.
10. The battery according to claim 1, wherein each of the positive
electrode mix and the negative electrode mix further comprises a
conductive additive.
11. A battery comprising: a positive electrode comprising: a positive
active material selected from the group consisting of LiNiCoAlO.sub.2,
LiMn.sub.2O.sub.4, LiNi.sub.yCo.sub.xM.sub.zO, where M.dbd.Mn, Al, Sn,
In, Ga or Ti and 0.15<x<0.5, 0.5<y<0.8 and 0<z<0.15,
Li[Li.sub.(1-2y)/3Ni.sub.yMn.sub.(2-y)/3]O.sub.2,
Li[Li.sub.(1-y)/3Co.sub.yMn.sub.(2-2y)/3]O.sub.2 and
Li[Ni.sub.yCo.sub.1-2yMn.sub.y]O.sub.2 where x=(2-y)/3 and 0<y<0.5,
LiNiCoO.sub.2.MnO.sub.2, lithium rich compounds
Li.sub.1+y(Ni.sub.1/3Co.sub.1/3Mn.sub.1/3).sub.1-yO.sub.2, where
y=(x/(2+x) and x=0-0.33, and xLi.sub.2MnO.sub.3(1-x)Li(NiCoMn)O.sub.2
and Li.sub.(1+y)(Ni.sub.0.5Co.sub.0.2Mn.sub.0.3).sub.1-yO.sub.2, where
y=(x/(2+x) and x=0-0.33, and LiMPO.sub.4, where M is one or more of the
first row transition-metal cations selected from the group consisting of
V, Cr, Mn, Fe, Co, Ni, and combinations thereof; a water soluble binder
comprising a (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer; and a conductive additive
selected from the group consisting of carbon black, acetylene black,
graphite, and combinations thereof; a negative electrode comprising: a
negative active material selected from the group consisting of graphite,
hard carbon, silicon, silicon alloy, tin, tin alloy, and lithium titanate;
a water soluble binder comprising the (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer; and the conductive additive; and
an electrolyte comprised of lithium salt in cyclic and linear carbonates.
12. The battery according to claim 11, wherein a mole ratio of
acrylonitrile units to acrylamide units is between about 3:1 and about
1:1.
13. The battery according to claim 11, wherein a mole ratio of styrene
units to butadiene units is between about 0.5:1.5 and about 1.5:0.5.
14. The battery according to claim 11, wherein an average molecular weight
of the polymer is between about 10,000 and 1,000,000.
15. The battery according to claim 14, wherein the average molecular
weight of the polymer is between about 100,000 and 200,000.
16. The battery according to claim 11, wherein the water soluble binder
is provided in the absence of a thickening agent.
Description
FIELD OF INVENTION
The present invention relates to a water soluble polymer binder for use
in a rechargeable lithium ion battery and the battery in which the binder
is used.
BACKGROUND
Rechargeable batteries use polymer binders to bind the active particulate
material together and adhere this particulate material to the current
collector in the fabrication of battery electrodes. The binder is
generally comprised of one or more polymers. The binders commonly used
in commercial li-ion batteries are polyvinyledene fluoride (PVDF),
ethylene-propylene and a diene (EPDM). These polymers are generally
insoluble in water and, thus are dissolved in an organic solvent such as
N-methyl pyrrolidone (NMP). The organic solvent additionally serves as
a dispersion medium for the active materials. Some disadvantages of using
organic solvents are that they have relatively high cost, can possess
negative environmental impacts, and pose disposal issues. Further, PVDF
is highly unstable and tends to break down at high temperatures.
Known water soluble binders, such as carboxy methyl cellulose (CMC),
require a thickening agent to control the viscosity of the binder. Further,
they exhibit only marginal adhesion capability. Polytetrafluoroethylene
(PTFE) based water soluble binders also exhibit poor adhesion and do not
exhibit good cycle life. Further, other known binders undergo hydrolysis
under acid or basic conditions. To avoid the hydrolysis and to improve
the dispersion, adhesion to the current collector, in a water-based
blending process, the pH must therefore be tightly controlled.
Accordingly, there is a need for a water soluble polymer binder in
rechargeable lithium batteries. This water soluble binder should exhibit
stability throughout a wide pH range, which results in greater ease in
preparing slurry for electrode fabrication.
SUMMARY
Briefly, the present invention provides an electrode comprising an
electro-active material, a (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer; and a conductive additive.
The present invention also provides a battery comprising a positive
electrode mix comprising a positive electrode active material and a water
soluble binder comprising a (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer. A negative electrode mix
comprises a negative electrode active material and a water soluble binder
comprising a (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer. The battery further comprises an
electrolyte.
Further, the present invention provides a battery comprising a positive
electrode comprising a positive active material selected from the group
consisting of LiNiCoAlO.sub.2, LiMn.sub.2O.sub.4,
LiNi.sub.yCo.sub.xM.sub.zO, where M.dbd.Mn, Al, Sn, In, Ga or Ti and
0.15<x<0.5, 0.5<y<0.8 and 0<z<0.15,
Li[Li.sub.(1-2y)/3Ni.sub.yMn.sub.(2-y)/3]O.sub.2,
Li[Li.sub.(1-y)/3Co.sub.yMn.sub.(2-2y)/3]O.sub.2 and
Li[Ni.sub.yCo.sub.1-2yMn.sub.y]O.sub.2 where x=(2-y)/3 and 0<y<0.5,
LiNiCoO.sub.2.MnO.sub.2, lithium rich compounds
Li.sub.1+y(Ni.sub.1/3Co.sub.1/3Mn.sub.1/3).sub.1-yO.sub.2, where
y=(x/(2+x) and x=0-0.33, and xLi.sub.2MnO.sub.3(1-x)Li(NiCoMn)O.sub.2
and Li.sub.(1+y)(Ni.sub.0.5Co.sub.0.2Mn.sub.0.3).sub.1-yO.sub.2, where
y=(x/(2+x) and x=0-0.33, and LiMPO.sub.4, where M is one or more of the
first row transition-metal cations selected from the group consisting of
V, Cr, Mn, Fe, Co, Ni, and combinations thereof, a water soluble binder
comprising a (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer, and a conductive additive
selected from the group consisting of carbon black, acetylene black,
graphite, and combinations thereof. A negative electrode comprises a
negative active material selected from the group consisting of graphite,
hard carbon, silicon, silicon alloy, tin, tin alloy, and lithium titanate.
The negative electrode further comprises a water soluble binder
comprising the (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer and the conductive additive. The
battery also includes an electrolyte comprised of lithium salt in cyclic
and linear carbonates or other solvents used in the Li-ion battery
electrolyte
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing summary, as well as the following detailed description of
the invention, will be better understood when read in conjunction with
the appended drawings. For the purpose of illustrating the invention,
there is shown in the drawing certain embodiments of the present invention.
It should be understood, however, that the invention is not limited to
the precise arrangements shown. In the drawings:
FIG. 1 is a schematic view of a battery formed in a jellyroll configuration
according to an exemplary embodiment of the present invention;
FIG. 1A is a schematic view of the battery of FIG. 1 with the electrolyte;
FIG. 2 is a cross-sectional representation of a prismatic electrochemical
cell according to an exemplary embodiment of the present invention; and
FIG. 3 is a schematic representation of a positive electrode, a separator
and a negative electrode-bi-cell configuration of the exemplary
embodiment illustrated in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In describing the embodiments of the invention illustrated in the drawings,
specific terminology will be used for the sake of clarity. However, the
invention is not intended to be limited to the specific terms so selected,
it being understood that each specific term includes all technical
equivalents operating in similar manner to accomplish similar purpose.
It is understood that the drawings are not drawn exactly to scale.
The following describes particular embodiments of the present invention.
It should be understood, however, that the invention is not limited to
the embodiments detailed herein. Generally, the following disclosure
refers to lithium ion batteries and a water soluble binder for use in
lithium ion batteries.
Referring to FIGS. 1 and 1A, a rechargeable lithium ion battery 100
according to an exemplary embodiment of the present invention includes
a positive electrode 112 formed from a positive electrode mix 110, a
negative electrode 122 formed from a negative electrode mix 120, and an
electrolyte 130. While FIG. 1 illustrates battery 100 formed in a
"jellyroll" configuration, those skilled in the art will recognize that
other formations, such as, for example, a prismatic configuration, which
is illustrated in FIG. 2, may also be used within the teaching of the
present invention.
Positive electrode mix 110 includes a positive electrode active material
selected from the group consisting of LiNiCoAlO.sub.2, LiMn.sub.2O.sub.4,
LiNi.sub.yCo.sub.xM.sub.zO, where M.dbd.Mn, Al, Sn, In, Ga or Ti and
0.15<x<0.5, 0.5<y<0.8 and 0<z<0.15,
Li[Li.sub.(1-2y)/3Ni.sub.yMn.sub.(2-y)/3]O.sub.2,
Li[Li.sub.(1-y)/3Co.sub.yMn.sub.(2-2y)/3]O.sub.2 and
Li[Ni.sub.yCo.sub.1-2yMn.sub.y]O.sub.2 where x=(2-y)/3 and 0<y<0.5,
LiNiCoO.sub.2.MnO.sub.2, lithium rich compounds
Li.sub.i+y(Ni.sub.1/3Co.sub.1/3Mn.sub.1/3).sub.1-yO.sub.2, where
y=(x/(2+x) and x=0-0.33, and xLi.sub.2MnO.sub.3(1-x)Li(NiCoMn)O.sub.2
and Li.sub.(1+y)(Ni.sub.0.5Co.sub.0.2Mn.sub.0.3).sub.1-yO.sub.2, where
y=(x/(2+x) and x=0-0.33, and LiMPO.sub.4, where M is one or more of the
first row transition-metal cations selected from the group consisting of
V, Cr, Mn, Fe, Co, Ni, and combinations thereof. In an exemplary embodiment,
the positive electrode active material is between about 80 and about 90
percent (by weight) of the positive electrode mix 110.
Positive electrode mix 110 may further include a conductive additive or
additives selected from the group consisting of carbon black, acetylene
black, graphite and combinations thereof. In an exemplary embodiment, the
conductive additive material is between about 0 and about 20 percent (by
weight) of the positive electrode mix 110.
Positive electrode mix 110 also includes a water soluble polymer
comprising a copolymer of (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide), and water. The binder is mixed with the
positive electrode active material, the conductive additive, and water
to form a slurry.
Polystyrenebutadiene rubber is less susceptible than other water soluble
binders to hydrolysis under acidic or basic conditions (i.e., pH less than
5 or greater than 10). It has been found that the combination of poly
(acrylonitrile-co-acrylamide) into the polystyrenebutadiene rubber,
forming a four-monomer-based copolymer, results in a water soluble binder
with even more stability than polystyrenebutadiene rubber over a broader
pH range. This attribute makes slurry preparation easier than when using
prior art water soluble binders because the pH of the slurry does not have
to be as tightly controlled throughout the blending process as it had in
prior art slurries.
An exemplary (polystyrenebutadiene rubber)-poly
(acrylonitrile-co-acrylamide) polymer has the chemical formula:
##STR00001## where a, b, m, and n are each greater than zero and are
percentages that add up to 100 percent (or "1"). In an exemplary embodiment,
a=b=m=n=0.25. In another exemplary embodiment, a>b and m>n. In an
exemplary embodiment, a=0.3, b=0.2, m=0.333, and n=0.167.
In an exemplary embodiment, the mole ratio of styrene units to butadiene
units (a:b) is between about 0.5:1.5 and about 1.5:0.5 and the mole ratio
of acrylonitrile units to acrylamide units (m:n) is between about 0.5:1.5
and about 1.5:0.5. Further, an exemplary mole ratio of
polystyrenebutadiene units to (acrylonitrile-co-acrylamide) units
(a+b):(c+d) is between about 0.25:0.75 and about 0.75:0.25.
In an exemplary embodiment, an average molecular weight of the polymer
is between about 10,000 and 1,000,000 and in another exemplary embodiment,
the average molecular weight of the polymer is between about 100,000 and
200,000.
In an exemplary embodiment, the water soluble binder is between about 1
and about 10 percent (by weight) of positive electrode mix 110.
The water soluble binder is used to make the slurry in the absence of a
thickening agent or any external reagent to control its viscosity. An
exemplary binder has a viscosity ranging between about 3,000 centipoise
and about 50,000 centipoise. The water soluble binder is also provided
in the absence of a wetting agent or any other additives to improve the
active material and conductive additive dispersion.
The slurry is coated on an aluminum current collector or a carbon coated
aluminum current collector to form positive electrode 112. The slurry pH
can range between about 7 and about 11.7 without significant reaction with
the current collector.
Negative electrode mix 120 comprises a negative electrode active additive
or additives material selected from the group consisting of graphite, hard
carbon, silicon, silicon alloy, tin, tin alloy, and lithium titanate. In
an exemplary embodiment, the negative electrode active material is
between about 80 and about 95 percent (by weight) of the negative electrode
mix 120.
Negative electrode mix 120 may further include a conductive additive
selected from the group consisting of carbon black, acetylene black,
graphite and combinations thereof. In an exemplary embodiment, the
conductive additive material is between about 0 and about 20 percent (by
weight) of the negative electrode mix 120.
Negative electrode mix 120 further comprises the water soluble binder as
described above with respect to the positive electrode mix 110. In an
exemplary embodiment, the water soluble binder is between about 1 and
about 10 percent (by weight) of the negative electrode mix 120. The binder
is mixed with the negative electrode active material, the conductive
additive, and water to form a slurry. The slurry is coated on a copper
current collector to form negative electrode 122.
An exemplary electrolyte 130 may be comprised of lithium salts such as
LiBF.sub.4, LiPF.sub.6, LiBOB, LiTFSI or LiFSI or mixtures thereof in
cyclic and linear carbonates or other solvent combinations
To form battery 100, after positive electrode 112 and negative electrode
122 are formed, positive electrode 112 and negative electrode 122 are each
then compressed or calendared for specific thickness. Electrodes 112, 122
are stacked as shown in FIG. 3, with separator 140 between each positive
electrode 112 and negative electrode 122. The stack is dried in a vacuum
oven until the moisture is below 2000 ppm, and most preferably below 200
ppm. The electrode may also be dried separately and stacked inside the
dry room. The electrode stack may be inserted into a polyethylene or
polypropylene cell housing 150, shown in FIG. 2, and filled with
electrolyte 130, forming battery 100. Battery 100 is then charged and
discharged to complete the forming process.
EXAMPLES
The following examples are given purely as an illustration and should not
be interpreted as constituting any kind of limitation to the invention.
The preparation of the binder was by water-phase precipitation
polymerization. K.sub.2S.sub.2O.sub.8--Na.sub.2S.sub.2O.sub.5 was used
as the initiator system in the presence of Fe.sup.2+. A round-bottom flask
was charged with a solution of 0.225 g (0.8 mmol) potassium persulfate,
0.105 g (0.6 mmol) sodium metabisulfite, and 1 ppm ferrous sulfate in 150
mL of deionized water. A solution of 18.44 g (0.177 mol) styrene, 9.58
g (0.177 mol) butadiene, 9.40 g (0.177 mol) acrylonitrile, and 12.59 g
(0.177 mol) acrylamide in 150 mL of deionized water was added to the
reaction mixture while being mixed with an overhead stirrer. The reaction
was conducted under a nitrogen atmosphere for 2 hours in a water bath
controlled at 50.degree. C. The polymer was then filtered and washed with
deionized water to remove the unreacted monomers and initiator. The yield
was about 53 percent.
The positive active material mix is prepared by mixing between about 10
and about 90 weight percent of active material, between about 0 and about
20 weight percent of conductive additive and between about 1 and about
10 weight percent of the binder polymer disclosed above, and water ranging
between 20 to 80 weight percent. High pH is a major problem in the positive
active materials, which contains mostly cobalt and nickel or combinations
thereof with other transition metals. To control the pH of the positive
active material slurry, diluted polymeric acid is added to the slurry very
slowly until the pH of the slurry was between about 7 and about 11.7, and
most preferably between about 7 and about 10. The reduced pH of the slurry
helps to improve the dispersion and the reaction with the current
collector is suppressed. Some examples of this carboxylic acid are:
Polylactic acid (PLA), Polyacrylic acid, Polysuccinic acid, poly maleic
acid and anhydride, poly furoic (pyromucic acid), poly fumaric acid, poly
sorbic acid, poly linoleic acid, poly linolenic acid, poly glutamic acid,
poly methacrylic acid, poly licanic acid, poly glycolic acid, poly
aspartic acid, Poly amic acid, poly formic acid, poly acetic acid, poly
propoionic acid, poly butyric acid, poly sebacic acid, and copolymers
thereof. The list of polymer acid examples may be equally applied to any
other exemplary embodiment(s) of this specification as suitable, and is
not exclusive.
The negative active mix is prepared by mixing between about 10 and about
95 weight percent active material, between about 0 and about 20 weight
percent of conductive additive and between about 1 and about 10 weight
percent of the binder polymer disclosed above. The negative electrode
slurry pH is between about 7 and about 10. pH control for the negative
active mix is not necessary. The electrolyte in the exemplary embodiment
was lithium salt in cyclic and linear carbonates.
The cells were built as described in FIGS. 1-3. The cells were then filled
with electrolyte 130.
While the principles of the invention have been described above in
connection with preferred embodiments, it is to be clearly understood that
this description is made only by way of example and not as a limitation
of the scope of the invention.
4 7,923,895 Electrochemical methods, devices, and structures
United States Patent
Chiang ,
7,923,895
et al.
April 12, 2011
Abstract
The present invention provides devices and structures and methods of use
thereof in electrochemical actuation. This invention provides
electrochemical actuators, which are based, inter-alia, on an electric
field-driven intercalation or alloying of high-modulus inorganic
compounds, which can produce large and reversible volume changes,
providing high actuation energy density, high actuation authority and
large free strain.
Inventors: Chiang; Yet-Ming (Framingham, MA), Hall; Steven R.
(Burlington, MA), Koyama; Yukinori (Cambridge, MA), Song;
Kyungyeol (Seoul, KR), Chin; Timothy E. (Cambridge, MA),
Rhyner; Urs (Schindellegi, CH), Sapnaras; Dimitrios (Baden
Wuerttemberg, DE), Tubilla; Fernando (Cambridge, MA)
Assignee: Massachusetts Institute of Technology (Cambridge, MA)
Appl. No.: 12/208,180
Filed:
September 10, 2008
Related U.S. Patent Documents
Application Number Filing Date Patent Number Issue Date<TD< TD>
11150477
Jun., 2005
7541715
<TD< TD>
60578855
Jun., 2004
<TD< TD>
60621051
Oct., 2004
<TD< TD>
Current U.S. Class:
310/311 ; 310/328
Current International Class:
H01L 41/08
Field of Search:
(20060101)
310/311,363
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Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 11/150,477,
filed Jun. 13, 2005, which claims priority from U.S. Provisional
Application Ser. No. 60/578,855, filed Jun. 14, 2004 and U.S. Provisional
Application Ser. No. 60/621,051, filed Oct. 25, 2004, which are hereby
incorporated in their entirety.
Claims
What is claimed is:
1. An electrochemical actuator, comprising: a. a negative electrode; b.
a positive electrode; and c. an intercalating species; wherein, when said
electrochemical actuator is subjected to an applied voltage or current,
or is permitted to discharge from an initially charged state,
intercalation or deintercalation of said species in at least one of the
electrodes of said actuator results in a volumetric or dimensional change
of said actuator and linear strain of at least 1% is produced.
2. The electrochemical actuator of claim 1, wherein said volumetric or
dimensional change is in said negative electrode, said positive electrode,
or a combination thereof.
3. The electrochemical actuator of claim 1, wherein said negative
electrode or positive electrode undergoes a phase change, anisotropic
expansion, or anisotropic contraction upon intercalation.
4. The electrochemical actuator of claim 1, wherein said negative
electrode, positive electrode, or combination thereof is lithium or a
lithium-metal alloy, which may be crystalline, nanocrystalline, or
amorphous.
5. The electrochemical actuator of claim 1, wherein an electrode comprises
carbon in the form of graphite, a carbon fiber structure, a glassy carbon
structure, a highly oriented pyrolytic graphite, a disordered carbon
structure, or a combination thereof.
6. The electrochemical actuator of claim 1, wherein the intercalating
species is an ion.
7. The electrochemical actuator of claim 1, wherein the intercalating
species is a proton, an alkali metal, or an alkaline earth metal.
8. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
aluminum, silver, gold, boron, bismuth, gallium, germanium, indium, lead,
antimony, silicon, tin, or a combination thereof.
9. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
aluminum.
10. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
silver.
11. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
gold.
12. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
boron.
13. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
bismuth.
14. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
gallium.
15. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
germanium.
16. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
indium.
17. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
lead.
18. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
antimony.
19. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
silicon.
20. The electrochemical actuator of claim 4, wherein said negative
electrode comprises lithium metal and said positive electrode comprises
tin.
Description
FIELD OF THE INVENTION
This invention provides devices and structures and methods of use thereof
in electrochemical actuation. This invention provides electrochemical
actuators, which are based, inter-alia, on an electric field-driven
intercalation or alloying of high-modulus inorganic compounds, which can
produce large and reversible volume changes, providing high actuation
energy density, high actuation authority and large free strain.
BACKGROUND OF THE INVENTION
Actuation is essentially a mechanism whereby a device is turned on or off,
or is adjusted or moved by converting various types of energies such as
electric energy or chemical energy into mechanical energy. Mechanical
energy can be stored as elastic energy in a material or a device, or can
be used to produce useful mechanical work, which is defined as the product
of stress and strain. Thus a useful measure of the potential for actuation
of a given material or device is the actuation energy density (energy per
unit volume). The actuation energy density is also useful for
distinguishing the capabilities of different actuation methods. The
specific (or gravimetric) energy is readily obtained from the energy
density knowing the density of the materials or device. While the "free
strain," or strain produced under zero or nearly zero stress conditions,
is sometimes used to characterize actuators or actuation materials, this
is an inadequate measure of actuation capability since no mechanical work
is done. Thus, the capability for mechanical work can only be known when
the strain produced against a known mechanical stress, or the stress
produced under known conditions of strain, are known.
Different types of actuators are categorized by the manner in which energy
is converted. For instance, electrostatic actuators convert
electrostatic forces into mechanical forces. Piezoelectric actuators use
piezoelectric material to generate kinematic energy. Electromagnetic
actuators convert electromagnetic forces into kinematic energy using a
magnet and coil windings.
Actuation, in theory, would find application in the production of adaptive
and morphing structures, though practically such an application has not
produced ideal results. Piezoelectric actuation provides high bandwidth
and actuation authority but low strain (much less than 1% typically), and
requires high actuation voltages. Shape memory alloys (SMAs),
magnetostrictors, and the newly developed ferromagnetic shape-memory
alloys (FSMAs) are capable of larger strain but produce slower responses,
limiting their applicability. Actuation mechanisms that are based on
field-induced domain motion (piezos, FSMAs) also tend to have low blocked
stress. All the above actuation methods are based on the use of active
materials of high density (lead-based oxides, metal alloys), which
negatively impacts weight-based figures of merit. Thus there is currently
a great need for a technology capable of providing high actuation energy
density, high actuation authority (stress), large free strain, and useful
bandwidth.
Certain methods of actuation using electrochemistry have previously been
described. For example, K. Oguro, H. Takenaka and Y. Kawami (U.S. Pat.
No. 5,268,082) have described using surface electrodes to create ion
motion under applied electric field across an ion-exchange membrane
resulting in deformation of the membrane. W. Lu, B. R. Mattes and A. G.
Fadeev (U.S. Patent Application No. 2002/0177039) have described using
ionic liquid electrolytes in conjugated polymers to obtain dimensional
change. R. H. Baughman, C. Cui, J. Su, Z. Iqbal, and A. Zhakidov (U.S.
Pat. No. 6,555,945) have used double-layer charging of high surface area
materials to provide for mechanical actuation. D. A. Hopkins, Jr. (U.S.
Pat. No. 5,671,905) has described an actuator device in which
electrochemically generated gas pressure is used to provide for
mechanical motion. H. Bauer, F. Derisavi-Fard, U. Eckoldt, R. Gerhrmann
and D. Kickel (U.S. Pat. No. 5,567,284) have similarly used
electrochemically-produced gas pressure in a pneumatic actuation device.
G. M. Spinks, G. G. Wallace, L. S. Fifield, L. R. Dalton, A. Mazzoldi,
D. De Rossi, I. I. Khayrullin, and R. H. Baughman (Advanced Materials,
2002, 14, No. 23, pp. 1728-1732) have described a pneumatic mechanism
using carbon nanotubes in which aqueous electrochemistry is used to
generate gas within a confined space allowing for mechanical motion. In
each of these non-faradaic approaches, the load-bearing actuation
materials are inherently a gaseous or liquid phase and may be expected
to have low elastic modulus and consequently low actuation energy density
and actuation stress, compared to the approach of the present invention.
With respect to solid-state electrochemistry, it is well-known to those
skilled in the art of solid state intercalation compounds, for instance,
those working in the battery field, that certain compounds undergo
expansion or contraction as their chemical composition is
electrochemically altered by ion insertion or removal (faradaic
processes). K. Takada and S. Kondo (Solid State Ionics, Vol. 53-56, pp.
339-342, 1992, and Japanese Patent Application 02248181) have further
demonstrated free strain in consolidated solid compounds undergoing
electrochemically induced composition change. They reported about 0.1%
free strain using Ag.sub.xV.sub.2O.sub.5 as a Ag intercalating compound,
which is a Level of strain comparable to that reached by many commercial
piezoelectric materials (e.g., those based on lead-zirconium-titanate
(PZT)). However, no mechanical load was provided and so mechanical work
was not demonstrated despite the observation of displacement. G. Cu, M.
Schmid, P.-W. Chiu, A. Minett, J. Fraysse, G.-T. Kim, S. Roth, M. Kolov,
E. Munoz and R. H. Baughman (Nature Materials, Vol. 2, pp. 316-319) have
used mattes of V.sub.2O.sub.5 nanofibres for actuation using aqueous
electrochemistry. In this instance, they reported strain under unloaded
conditions of up 0.21%, and the production of stress under nominally
zero-strain conditions of up to 5.9 MPa, although whether the process used
to generate the stress was faradaic or non-faradaic was not known.
SUMMARY OF THE INVENTION
The invention provides, in one embodiment, an electrochemical actuator,
comprising an negative electrode, a positive electrode and an
intercalating species, wherein the electrochemical actuator is subjected
to an applied voltage, whereby application of the voltage or cessation
thereof induces intercalation of the intercalating species in the
actuator, resulting in a volumetric or dimensional change of the actuator
under conditions of mechanical constraint or loading resulting in the
production of useful mechanical energy.
In another embodiment, the invention provides a Multilayer Stacked
Electrochemical Actuator, comprising two or more negative electrode
layers, two or more positive electrode layers, and an intercalating
species, wherein the Multilayer Stacked Electrochemical Actuator is
subjected to an applied voltage, whereby application of the voltage or
cessation thereof induces intercalation of the intercalating species in
the actuator, resulting in a volumetric change of the actuator resulting
in the production of useful mechanical energy.
In another embodiment, the invention provides a Rotational
Electrochemical Actuator, comprising rolled layers of an negative
electrode, a positive electrode and an intercalating species, wherein the
rolled layers assume a laminate configuration, and wherein the Rotational
Electrochemical Actuator is subjected to an applied voltage, whereby
application of the voltage produces intercalation of the intercalating
species in the actuator, resulting in a volumetric or dimensional change
of the actuator such that the rolled laminate configuration winds or
unwinds, and torque is produced.
In one embodiment, following when the rolled laminate configuration winds
or unwinds, rotary motion is produced. In one embodiment, the rotary
motion ranges from 1-360.degree.. In another embodiment, the rotary
motion produces 1 or more rotations. In another embodiment, the 1 or more
rotations are complete or incomplete. In another embodiment, the rotation
is in a clockwise direction or counter clockwise direction, or a
combination thereof.
In another embodiment, the invention provides a Continuous Fiber
Electrochemical Actuator, comprising a fibrous electrode, a counter
electrode and an intercalating species wherein the Continuous Fiber
Electrochemical Actuator is subjected to an applied voltage, whereby
application of the voltage or its cessation induces intercalation of the
intercalating species in the actuator, resulting in a volumetric or
dimensional change of the actuator, such that said fibrous negative
electrode undergoes elongation and produces useful mechanical work. In
one embodiment, the volumetric or dimensional change is induced in tension
as well as in compression.
In another embodiment, the Continuous Fiber Electrochemical Actuator is
comprised of multiple coated fibers, which are utilized to form a fiber
composite. In another embodiment, the composite further comprises a
matrix, which, in another embodiment, is a polymer. In another embodiment,
the composite of the Continuous Fiber Electrochemical Actuator comprises
fiber ends, which are uncoated. In another embodiment, the uncoated ends
of the fibers enable electrical connections to be applied to the ends of
the fibers.
In another embodiment, the Continuous Fiber Electrochemical Actuator
comprises multiple layers, which, in another embodiment are assembled in
parallel or in perpendicular orientation. In another embodiment, the
perpendicular orientation allows positive and negative shearing
actuation of the actuator, which, in another embodiment, produces torque,
or, in another embodiment, produces rotation. In another embodiment, the
perpendicular orientation allows for charge transfer between layers when
low voltage is applied.
In one embodiment of the invention, intercalation of the species in an
actuator of this invention can occur upon both application of the voltage
and cessation thereof. In another embodiment, the extent of volume change
is controlled by controlling the amount of current flow into or out of
the actuator. In another embodiment, the volumetric or dimensional change
is in the negative electrode or positive electrode or a combination
thereof. In another embodiment, the volumetric or dimensional change is
reversible. In another embodiment, the intercalation produces high strain
against a substantial mechanical load. In another embodiment, the
negative electrode, or in another embodiment, the positive electrode,
serves as a donor or acceptor or combination thereof of the intercalating
species.
In another embodiment, an electrode of an actuator of this invention is
initially enriched in, and may serve as a source for, the intercalating
species. In another embodiment, a negative electrode of an actuator of
this invention may serve as a source for the intercalating species. In
another embodiment, a positive electrode of an actuator of this invention
may serve as a source for the intercalating species.
In another embodiment, the electrode comprises a high elastic modulus
compound. In another embodiment, an electrode comprises an ion transition
metal oxide. In another embodiment, the ion in said ion transition metal
oxide is a proton or an alkali metal or an alkaline earth metal. In another
embodiment, the alkali metal is lithium. In another embodiment, an
electrode comprises: LiCoO.sub.2, LiFePO.sub.4, LiNiO.sub.2,
LiMn.sub.2O.sub.4, LiMnO.sub.2, LiMnPO.sub.4, Li.sub.4Ti.sub.5O.sub.12,
and their modified compositions and solid solutions. In another
embodiment, an electrode comprises: an oxide compound comprising one or
more of titanium oxide, vanadium oxide, tin oxide, antimony oxide, cobalt
oxide, nickel oxide or iron oxide. In another embodiment an electrode
comprises TiSi.sub.2, MoSi.sub.2, WSi.sub.2, and their modified
compositions and solid solutions. In another embodiment an electrode
comprises a metal or intermetallic compound. In another embodiment an
electrode is lithium or a lithium-metal alloy, which may be crystalline,
nanocrystalline, or amorphous. In another embodiment the negative
electrode is one or more of aluminum, silver, gold, boron, bismuth,
gallium, germanium, indium, lead, antimony, silicon, or tin. In another
embodiment, an electrode is carbon in the form of graphite, a carbon fiber
structure, a glassy carbon structure, a highly oriented pyrolytic
graphite, a disordered carbon structure or a combination thereof. In
another embodiment, the intercalating species is an ion. In another
embodiment, a proton or an alkali metal or an alkaline earth metal.
In another embodiment, the negative electrode or positive electrode
compound undergoes anisotropic expansion or contraction upon
intercalation.
In another embodiment, the compound is textured or oriented in the
electrodes of the actuator resulting in anisotropic expansion or
contraction. In another embodiment, the compound is oriented in the
electrodes of the actuator to increase the dimensional change in the
primary actuation direction of the actuator upon intercalation or
alloying. In another embodiment, the negative or positive electrode
compound undergoes a phase change upon intercalation or de-intercalation.
In another embodiment, the negative or positive electrode material is in
the form of a single crystal, polycrystal, or fine powder. In another
embodiment the fine powder is of anisometric particle shape. In another
embodiment the fine powder has a platelet or rod-like morphology. In
another embodiment the smallest dimension of the powder particles is on
average less than about 100 micrometers.
In another embodiment, one or more electrodes of the actuator comprise
a porous sintered aggregate of the negative or positive electrode compound.
In another embodiment, the porous sintered aggregate is a composite
comprising also a conductive additive or sintering aid. In another
embodiment the sintered aggregate has crystallites of an electrode
compound that share a common orientation or texture of their crystal axes,
which in one embodiment is uni-axial, and in another embodiment is biaxial.
In another embodiment, one or more electrodes of the actuator comprise
a composite containing a powder of the negative or positive electrode
compound, an organic or inorganic binder, and optionally a conductive
additive. In one embodiment the binder is a polymer, and the conductive
additive is carbon. In another embodiment, the volume percentage of the
electrode compound in the electrode is at least 45%. In another embodiment
the particles of the compound are anisometric in shape, and have a
preferred common orientation. In another embodiment, the particles of the
compound are crystalline, and have a preferred common orientation or
texture of their crystal axes, which in one embodiment is uni-axial, and
in another embodiment is biaxial. In another embodiment, the composite
electrode is fabricated by mixing its constituents in an aqueous or
inorganic solvent, coating and drying the mixture, and pressing or
calendaring the coating.
In another embodiment, an actuator of this invention further comprises
a current collector, which, in another embodiment, comprises a conductive
material. In another embodiment, an actuator of this invention further
comprises a separator, which in one embodiment is porous, or in another
embodiment, is rigid. In one embodiment, the porous separator comprises
a microporous polymer. In another embodiment, the porous separator
comprises a porous electronically insulating ceramic material, which in
another embodiment is alumina, an aluminosilicate, cordierite, or a
silicate glass.
In another embodiment, an actuator of this invention further comprises
an electrolyte. In one embodiment, the electrolyte is a solid electrolyte,
which in one embodiment is a polymer, and in another embodiment an
inorganic crystal or glass. In another embodiment, the electrolyte is a
liquid or gel electrolyte. In another embodiment, an actuator of this
invention further comprises an external packaging layer, which may be,
in one embodiment, an electrochemically-insulating layer, or, in another
embodiment, a protective layer or, in another embodiment, a combination
thereof.
In another embodiment, this invention provides an actuator device in which
an electrochemical actuator of this invention is further used in an
actuator structure that provides for stress amplification (strain
deamplification) or stress deamplification (strain amplification).
In another embodiment, an electrochemically-actuated strain deamplifying
(stress amplifying) actuator device having a woven structure is provided.
In another embodiment, an electrochemically-actuated strain amplifying
(stress deamplifying) lever actuator is provided.
In another embodiment, this invention provides a structure or apparatus
comprising an actuator of this invention. In one embodiment, the structure
or apparatus is adaptive. In another embodiment, the actuator is used as
an element to apply stress at a site on the structure or apparatus that
is distal to the actuator. In another embodiment, the apparatus amplifies
the volumetric or dimensional change induced by the actuator, while in
another embodiment, the apparatus deamplifies the volumetric or
dimensional change induced by the actuator.
In one embodiment, the structure or apparatus moves in or beyond the
atmosphere. In one embodiment, such a structure or apparatus may be an
aircraft, a missile, a spacecraft or a satellite. In another embodiment,
such a structure or apparatus may be part of an aircraft, a missile, a
spacecraft, a worm, a robot or a satellite. In other embodiments, the part
may be a wing, a blade, a canard, a fuselage, a tail, an aileron, a rudder,
an elevator, a flap, a pipe, a propellor, a mirror, an optical element,
or a combination thereof. In other embodiments, the part may be an engine,
a motor, a valve, a regulator, a pump, a flow control device, a rotor,
or a combination thereof.
In another embodiment, the structure or apparatus moves in water. In one
embodiment, such a structure or apparatus may be a boat, a ship, a
submarine or a torpedo. In another embodiment, the structure or apparatus
is a part of a boat, a ship, a submarine or a torpedo. In another embodiment,
the part is a blade, a rudder, a pipe, a propellor, an optical element,
or a combination thereof. In another embodiment, the part is an engine,
a motor, a valve, a regulator, a pump, a flow control device, a rotor,
a switch or a combination thereof.
In another embodiment, the structure or apparatus is a bomb, a means of
transportation, an imaging device, a robotic, a worm, a prosthesis, an
exoskeleton, an implant, a stent, a valve, an artificial organ, an in vivo
delivery system, or a means of in vivo signal propagation.
In another embodiment, this invention provides a method of actuation,
comprising the step of applying a voltage or current to an actuator
comprising a negative electrode, a positive electrode and an
intercalating species, wherein controlling the applied voltage or current
induces intercalation of the intercalating species in the actuator,
whereby the intercalation induces a volumetric or dimensional change of
said actuator. In one embodiment, an apparatus or structure comprises the
actuator. In one embodiment, the method results in a structural change
in the structure or apparatus comprising the actuator. In another
embodiment, the structure or apparatus comprises more than one actuator.
In another embodiment, a curvature, bend or twist, or combination thereof
is induced in the structure or apparatus.
In another embodiment, this invention provides a method of producing
torque or rotary motion in an apparatus comprising a Rotational
Electrochemical Actuator, comprising the step of applying a voltage to
a Rotational Electrochemical Actuator comprising an negative electrode,
a positive electrode and an intercalating species, wherein applying
voltage causes current flow inducing intercalation of the intercalating
species in the actuator resulting in a volumetric or dimensional change
of the actuator such that the rolled laminate layers unwind, and torque
or rotary motion is produced.
In another embodiment, this invention provides a pump comprising at least
one electrochemical actuator, comprising an negative electrode, a
positive electrode, an intercalating species, and at least one valve,
wherein following application of a voltage causing current flow in said
actuator, intercalation of said species produces a change in volume in
said actuator, such that fluid is directed through said valve. In one
embodiment, the pump comprises a series of actuators. In one embodiment,
the actuators are placed in a parallel series. In another embodiment, the
actuators are placed in a plane so as to direct fluid through designed
channels.
In another embodiment, this invention provides a nastic structure
comprising at least one electrochemical actuator, comprising an negative
electrode, a positive electrode, and an intercalating species, wherein
following application of a voltage causing current flow in the actuator,
intercalation of the intercalating species produces a change in volume
in the actuator, such that a bend or other deformity is induced in the
nastic structure.
In another embodiment, this invention provides for the use of an
electrochemical actuator in a microfluidic system, wherein a network of
hydraulic actuators is driven by intercalation-induced volume changes in
the electrochemical actuator.
In another embodiment, this invention provides for the use of at least
one electrochemical actuator for flight control of an aircraft, wherein
the actuator is positioned on the aircraft, such that following
intercalation-induced volume changes in the actuator(s), greater flight
control is achieved.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A demonstrates an embodiment of a reversible lithium intercalation
with phospho-olivines Li(Fe,Mn)PO.sub.4 to produce large intrinsic
(crystallographic) volume changes of 7.4-10% [A. Yamada et al., J.
Electrochem. Soc., 148, A224 (2001)]. FIG. 1B depicts the expansion upon
discharge detected following Li+ intercalation into an LiFePO.sub.4
positive electrode in an actuator with a 100 .mu.m active layer, producing
a 2.3% linear strain, well in agreement with the predicted value, in this
embodiment of the invention. FIG. 1C depicts the actuation strain in a
multilayer Li-polymer battery of .about.5 mm thickness. Strain was
measured normal to the plane of the multilayer stack during charge and
discharge. The 50 mm reversible displacement corresponds to .about.1%
linear strain.
FIG. 2 demonstrates an embodiment of a multilayer stacked electrochemical
actuator comprised of Li ion-polymer batteries (ATL Corporation).
According to this aspect of the invention, the elastic (Young's) modulus
measured normal to the face of the cells (in the direction of layer
stacking) was very low, .about.30 MPa.
FIG. 3 graphically depicts the charge-discharge voltage curves and
corresponding strain, obtained under various pre-stress conditions, for
actuators of one embodiment of a multilayer stacked design. Maximum strain
was .about.0.7% and obtained actuation energy density was .about.12
kJ/m.sup.3.
FIG. 4 graphically depicts the charge-discharge voltage curve and
corresponding strain, obtained under 3.5 MPa constant pre-stress, for
actuators of one embodiment of a multilayer stacked design. Strain
is .about.1% and actuation energy density is .about.35 kJ/m.sup.3.
FIG. 5 shows embodiments of lithium ion rechargeable cells based on
LiCoO.sub.2-carbon chemistry, with different internal constructions.
FIG. 6 graphically depicts the volume reduction of an embodiment of a
multilayer stacked actuator cells prior to and following isopressing
treatment at 45,000 psi.
FIG. 7 graphically depicts viscoelastic relaxation of applied stress in
an embodiment of a multilayer stacked actuator. Relaxation in applied
stress is measured as a function of time in cells subjected to 10 MPa stress
in an Instron test machine.
FIG. 8 graphically depicts the volume expansion of an embodiment of a
multilayer stacked actuator having 150 mAh charge capacity, measured by
fluid displacement.
FIG. 9 graphically depicts the cyclic charge/discharge and corresponding
strain of two embodiments of multilayer stacked actuators under 5 MPa
uniaxial stress.
FIG. 10 graphically depicts the cyclic actuation tests of an embodiment
of a multilayer stacked actuator at 5 and 10 MPa uniaxial stress.
FIG. 11 graphically depicts the cyclic actuation tests of an embodiment
of a multilayer stacked actuator at 15 and 20 MPa uniaxial stress.
FIG. 12 graphically depicts the strain and energy density of embodiments
of multilayer stacked actuators as a function of uniaxial prestress.
FIG. 13 graphically depicts strain versus cycle number for constant
current cycling of an embodiment of a multilayer stacked actuator at the
given current for 1 and 2 minutes under 2 MPa constant stress.
FIG. 14 graphically depicts strain versus cycle number for constant
current cycling of a multilayer stacked actuator at the given current for
5 and 10 minutes under 2 MPa constant stress.
FIG. 15 shows strain versus the utilized reversible capacity in an
embodiment of a multilayer stacked actuator under 2 MPa constant stress.
FIG. 16 depicts an embodiment of a bi-layer stacked actuator fabricated
from densified single-layer coatings of LiCoO.sub.2 and graphite
electrodes.
FIG. 17 graphically depicts a charge-discharge voltage curve and
corresponding strain measured in an embodiment of a bi-layer stacked
actuator under 1 MPa constant prestress. Measured strain is 3-4% and
actuation energy density is .about.45 kJ/m.sup.3.
FIG. 18 graphically depicts a charge-discharge voltage curve and
corresponding strain measured in an embodiment of a bi-layer stacked
actuator under 10 MPa constant pre-stress. Measured strain is 2.5-3% and
actuation energy density is .about.300 kJ/m3.
FIG. 18 shows actuation strain versus charge/discharge for bilayer
stacked actuator, at 10 and 17 MPa applied uniaxial stress.
FIG. 19 shows actuation strain versus charge/discharge for an embodiment
of a bilayer stacked actuator, at 10 and 17 MPa applied uniaxial stress.
FIG. 20 shows strain versus charge and discharge at 1 MPa stress in an
embodiment of a multilayer actuator, 6 mm thick, utilizing high density
electrodes and a microporous polymer separator.
FIG. 21 shows strain versus charge and discharge at 5 MPa stress in an
embodiment of a multilayer actuator, 6 mm thick utilizing high density
electrodes and microporous polymer separator.
FIG. 22 shows strain versus charge and discharge at 10 MPa in an embodiment
of a multilayer actuator, 6 mm thick, utilizing high density electrodes
and microporous polymer separator.
FIG. 23 depicts an embodiment of an actuator comprising multiple square
posts laser-micromachined from electrochemical actuation material, here
highly oriented pyrolytic graphite (HOPG) with the c-axis direction
aligned with the post axis (longitudinal direction). An LiCoO.sub.2
lithium source is placed adjacent to HOPG posts allowing intercalation
of the graphite in the transverse direction, in this embodiment.
FIG. 24 graphically depicts the actuation strain measured upon
intercalation of lithium into one embodiment of an HOPG-based actuator
under 100 MPa constant pre-stress. Actuation energy density
is .about.1000 kJ/m.sup.3.
FIG. 25 is an SEM image of an array of posts machined in a piece of HOPG
forming active elements of an embodiment of an electrochemical actuator,
and schematic side view of the actuator assembly.
FIG. 26 shows strain versus discharge/charge voltage for an HOPG actuator
under 100 MPa applied stress (1 metric ton per cm2) (A), and strain versus
charging voltage for an HOPG laser micromachined actuator under 50 MPa
applied stress (B).
FIG. 27 schematically depicts an embodiment of an alternate post design
for a multi-post actuator.
FIG. 28 schematically depicts an embodiment of a large stroke
electrochemical lever actuator.
FIG. 29 schematically depicts an embodiment of a large stroke
electrochemical lever actuator.
FIG. 30 schematically depicts views of weave actuator with main parts:
(1) active elements, (2) top and bottom fibers and (3) constant-curvature
caps.
FIG. 31 depicts an experimental setup for a test of an embodiment of an
electrochemical woven actuator and results from test, with actuator
strain and active element strains shown.
FIG. 32 graphically depicts the theoretical stiffness and maximum-strain
bounds of an embodiment of the EWA as a function of the ratio of its length
(L) and the active element length (w). Actual test results are shown as
stars on the figure.
FIG. 33 depicts an embodiment of an actuated beam utilizing 27
electrochemical actuators of type shown in FIGS. 2-4, electrically
connected in parallel. Layers of fiberglass weave constrain the
deformation of the beam on the lower surface. When one end (the base) of
the beam was clamped, the tip of the beam was observed to deform 1 mm upon
charging or discharging the batteries, corresponding to a surface strain
of 400 microstrain.
FIG. 34 schematically depicts actuation in a fluidic system, comprising
an electrolytic membrane, which pumps an ion from one side to another,
producing high actuation forces. In one embodiment, R1 is not equal to
R2.
FIG. 35 schematically depicts an example of an actuator comprising a
positive electrode, separated from an negative electrode by a separator,
where the height of the actuator is 200 .mu.m.
FIG. 36 is an additional schematic depiction of one embodiment of this
invention, showing an actuator 10 comprising a positive electrode 12, in
this case LiMPO.sub.4, where M is any metal, separated from an negative
electrode 14 by a separator layer 16, and both negative electrode and
positive electrode current collectors, 18 and 20, respectively, attached
to a power source 22, supplying 4 V. The actuator possesses 200 .mu.m stack
thickness, and an E value of 2.times.10.sup.4 V/m.
FIG. 37 schematically depicts one embodiment of a solid-state thin-film
battery (24) that can be used for actuation. The negative electrode 28
is separated from the positive electrode 30 by an electrolyte layer 32,
and current collectors for the negative electrode 34 and positive
electrode 36 as well as the other components of the actuator are positioned
on a substrate 26. A protective coating 38 covers the actuator, providing
a height of 15 .mu.m, in this example.
FIG. 38 schematically depicts embodiments of a Multilayer Stacked
Actuator of this invention. In this example, a high stiffness bilayer
subassembly 40 and multilayer-stacked assembly 54 are depicted. Because
the system is composed of ceramic layers 44, 46 and metal electrodes 42,
the stack will have high stiffness and a strain capability of several
percent. Liquid electrolyte may infiltrate the actuator 48. Current
collectors 38, 50 may be present, with a power source 52, as indicated.
This actuator would be an all-purpose, high energy density actuator, which
could be used in many applications requiring high energy densities at
modest bandwidth.
FIG. 39 schematically depicts a Rotational Electrochemical Actuator 56,
comprising laminates of current collectors 58, negative electrodes 60,
positive electrodes 62, and a separator 64. A structural aluminum layer
66 is added and the Rotational Electrochemical Actuator is infiltrated
with electrolyte 68. The actuator may be assembled as a spiral 70, around
an inner mandrel 72, and covered by an outer shell 74.
FIG. 40 schematically depicts an embodiment of a Continuous Fiber
Electrochemical Actuator 76 comprised of a fiber composite system, in
which the active fibers form the negative electrode 78. The fiber negative
electrode is separated from the positive electrode 80, by a polymer or
inorganic separator 82, and a liquid or solid electrolyte layer 84.
Current collectors 86 and 88, respectively, are connected to the power
source 90 in the actuator.
FIG. 41 schematically represents another embodiment of a Continuous Fiber
Electrochemical Actuator 92 comprised of individual negative electrode
fibers 94, coated with a ceramic or polymer electrolyte 96 and a lithiated
positive electrode 98, connected to a power supply 100. These fibers can
form an active fiber composite 102.
FIG. 42 depicts an embodiment of an adaptive structure or apparatus 104
comprising an electrochemical actuator of this invention 106, mounted on
its surface 108 (FIG. 10A). In one embodiment, the integration of an
actuator within a structure or apparatus 110 may be as schematically
depicted in FIG. 10B. The electrochemical actuator, or in another
embodiment, actuators 140, may be in one embodiment, thin film, or in
another embodiment, thick film laminated electrochemical actuators,
which may be oriented normally to the surface, and may be positioned within
a stiff surface layer 120, on a substrate 130. Changing the aspect ratio
of the expanding and contracting elements of the actuators and strategic
positioning may produce greater deformation in the surface plane, in
another embodiment, as schematically diagrammed in FIG. 10C, via the
positioning of the positive electrode 150 and the negative electrode 160,
in another embodiment, which may be evident when viewed looking down the
plane of the surface, or in cross-section (10D).
FIG. 43A schematically depicts one embodiment of an actuator 170
comprising a carbon or lithium negative electrode 200, which expands when
lithiated, and a LiMn.sub.2O.sub.4 or LiFePO.sub.4 positive electrode 190,
which contracts when de-lithiated, which if bonded to a separator 180,
will produce a marked bend in the entire structure. One embodiment of such
a use would be in an airfoil 210 where the actuator is positioned, such
that the negative electrode is facing outward 230, from the surface 220,
such that following actuation, a greater curvature outward occurs (43B).
FIG. 44C schematically depicts a structure 240 comprising a silicon wafer
250 that can be lithiated from the surface 260, via the lithium metal or
lithiated oxide electrode as the lithium source, in order to induce
volumetric expansion hence bending.
FIG. 44A schematically depicts one embodiment of a structure or apparatus
280 made to bend around more than one axial direction, by having an array
of electrochemical actuators 300 on the surface of the structure or
apparatus 290. FIG. 44B depicts an example of how actuators may be utilized
to unfurl a wing.
FIG. 45 schematically depicts an assembly 310 of possible arrangements
of actuators 320 on the wings 330 of an aircraft, which may provide twist
to the wing.
FIG. 46A schematically depicts a microfluidic pump 340, comprising a
positive electrode 350, and negative electrode 360, separated by a liquid
electrolyte layer 370. The actuator undergoes a net volume change upon
charging and discharging 390, enabling fluid propulsion through the
valves 380. A pump or microfluidic device 400 comprising a series of
actuators 410, which upon charging and discharging induces fluid flow from
intake 420, through exit 430 of the pump (B). Positioning of the actuators
is such that channels are designed (14C).
FIG. 47 schematically depicts multiple morphing capabilities of the
actuators or structures comprising the same of this invention.
FIG. 48 depicts embodiments of a morphing plate architecture envisioned
for this invention. In A, an overall plate architecture, with 3 actuator
orientations is shown. In B, an embodiment depicting an embedded
individually addressable multilayer stack actuator array is shown. In C,
an embodiment depicting a distributed array of electrochemical fiber
actuators applying tensile loads is shown. In D, embodiments depicting
actuator designs, which allow for greater expansion or contraction, are
shown.
DETAILED DESCRIPTION OF THE INVENTION
This invention provides, in one embodiment, methods and
structures/apparatuses for actuation that is based on the electric field
driven intercalation (ion-exchange) of high-modulus inorganic compounds
and produces true, useful, mechanical work.
The invention provides, in one embodiment, an electrochemical actuator,
comprising a negative electrode, a positive electrode and an
intercalating species, wherein the electrochemical actuator is subjected
to an applied voltage or current, whereby application of the voltage or
current or cessation thereof induces intercalation of the intercalating
species in the actuator, resulting in a volumetric or dimensional change
of the actuator. In the context of this invention, and in one embodiment,
intercalation is understood to have a broad meaning including the
insertion of ions into a structure causing a dimensional change without
substantially changing the arrangement of other atoms, insertion forming
a disordered or ordered solid solution, insertion forming an alloy, or
insertion causing a partial or complete transformation to a new phase.
All of these methods of "intercalation" may be useful in providing
mechanical actuation.
Solid-state ion insertion compounds used in battery systems may undergo
large and reversible volume changes (up to .about.15% with high
reversibility) as ions (e.g., Li+) are intercalated into the structure,
which is exploited by the actuators of this invention, in one embodiment.
As one example, FIG. 1 shows the volume changes that occur in the olivine
structure compound (Fe,Mn)PO.sub.4 as it is lithiated to the endmember
composition Li(Fe,Mn)PO.sub.4. Between the fully lithiated (upper curve)
and fully delithiated (lower curve) limits of composition, a volume change
of 7.4-10% (linear strain of 2.4-3.2%) is realizable depending on the
Fe/Mn ratio. This is just one of numerous new intercalation compounds that
have emerged from the battery field, which have promise for the technology
here proposed, all of which represent embodiments of this invention. The
insertion of ions into such compounds can result in volume expansion or
contraction, and such expansion or contraction can be isotropic or
anisotropic.
The volume change may have a corresponding linear or multiaxial
dimensional change that is here exploited for mechanical actuation. Where
the dimensional change is anisotropic, the anisotropy may be further
exploited to maximize, minimize, or optimize the dimensional change for
actuation, by using said compounds in a form in which there is a
crystallographic orientation of the compound in the desired directions
of actuation. For example, in one embodiment in which graphite is the
active material, the expansion upon intercalation of alkali ions occurs
primarily normal to the graphene planes of the graphite structure, and
maximum expansion and contraction can be produced by having the graphene
planes of the graphite oriented in the desired directions of actuation.
Table 1 provides exemplary pairs of compounds comprising an
electrochemical couple with reversible electrochemical insertion of
lithium, for which values for intrinsic linear and volumetric expansions
(i.e., crystal constants of the lithiated and delithiated forms) are
available. Table 2 provides exemplary individual compounds used as
positive and negative electrodes in lithium batteries, and the volume
change that occurs for a typical composition to which the compound can
be delithiated. Note that in the electrochemical actuators of this
invention, compounds are not restricted to being used as the electrode
that they would comprise in a battery designed for optimal energy storage;
that is, the active materials may comprise either positive or negative
electrode in an electrochemical actuator.
TABLE-US-00001 TABLE 1 Cell Voltage and Net Volume Change For
Charge-Balanced Cells Using Graphite as One Electrode Net Volume Change
Electrochemical Charging Cell (Positive electrode + Reaction for Cell
Voltage Negative electrode) LiCoO.sub.2 + 3C Li.sub.0.5CoO.sub.2 +
0.5LiC.sub.6 3.6 V +5.8% LiNiO.sub.2 + 4.2C Li.sub.0.3CoO.sub.2 +
0.7LiC.sub.6 3.7 V +5.3% LiFePO.sub.4 + 6C FePO.sub.4 + LiC.sub.6 3.3 V
+5.8% LiMn.sub.2O.sub.4 + 6C Mn.sub.2O4 + LiC.sub.6 3.8 V +4.2% Li + 6C
LiC.sub.6 0.15 V -2.4%
TABLE-US-00002 TABLE 2 Selected Lithium Storage Electrodes and Associated
Volume Changes Lithium Insertion Limiting Compound
Composition* .DELTA.V/V.sub.0 Comments Positive electrodes LiCoO.sub.2
Li.sub.0.5CoO.sub.2 +1.85% Y~400 GPa. LiFePO.sub.4 FePO.sub.4 -7.35%
Y~150 GPa. LiNiO.sub.2 Li.sub.0.3NiO.sub.2 -2.82% LiMn.sub.2O.sub.4
Mn.sub.2O.sub.4 -7.35% Negative electrodes Li.sub.4/3Ti.sub.5/3O.sub.4
Li.sub.7/3Ti.sub.5/3O.sub.4 0 "Zero-strain" spinel structure electrode.
C 1/6 LiC.sub.6 +13.1% Y~15 GPa (polycrystal). Si Li.sub.4.4Si
+312% .beta.-Sn Li.sub.4.4Sn +260% *For reversible cycling, except for
Si and Sn
LiCoO.sub.2, when used as the positive electrode, expands 1.85% when
lithium is removed, while most other compounds shrink. Despite a modest
volume change, LiCoO.sub.2 is of interest because it can be used with
carbon (Table 1) in a highly reliable and well-developed electrochemical
system. LiCoO.sub.2 has a hexagonal structure (rhombohedral space group
R-3m) in which the lithium planes are parallel to the c-axis. The Young's
modulus along the c-axis is 330 GPa while that along the a-axis (which
lies in the fast-diffusion plane) is 500 GPa (F. X. Hart and J. B. Bates,
J. Appl. Phys., 83[12], 7560 (1998)), hence an aggregate value for
randomly-oriented polycrystals of .about.400 GPa can be obtained. Such
a value is close to that obtainable for high strength structural ceramics
such as Al.sub.2O.sub.3 and SiC.
A second example for use as the positive electrode is LiFePO.sub.4, a
phospho-olivine that when suitably doped (S. Y. Chung, J. T. Bloking, Y.-M.
Chiang, Nature Materials, 1, 123 (2002)) has extremely fast
charge-discharge behavior for a lithium battery, retaining .about.50% of
its charge capacity (and crystal expansion) at charge-discharge times
of .about.1 min (17 mHz). Its elastic properties have not been measured,
but the similar mineral phosphate apatite (Ca.sub.5(OH, F)(PO4).sub.3)
has a Young's modulus of 150 GPa (G. Simmons and H. Wang, Single Crystal
Elastic Constants and Calculated Aggregate Properties, MIT Press,
Cambridge, Mass., 1971). It is expected that the phospho-olivines will
have a higher modulus than apatite due to their denser atomic packing.
Another attraction of these compounds is their safety in electrochemical
systems.
As shown in Table 2, graphite is an excellent candidate for use as the
negative electrode of an electrochemical actuator, owing to
its .about.13% volume expansion upon lithiation to the limiting
composition LiC.sub.6. This family includes not just graphite but also
various other forms of disordered carbons, which together constitute
widely used negative electrodes in current technology (see for example
N. Imanishi, Y. Takeda and O. Yamamoto, and by M. Winter and J. O. Besenhard,
Chapters 5 and 6 respectively in Lithium Ion Batteries, Eds. M. Wakihara
and O. Yamamoto, Wiley-VCH, Weinheim, Germany, 1998)).
Using materials from Table 2, several types of electrochemical actuators
are conceived. In one, the volume change of one electrode material is used
to perform mechanical work, while the volume change in the
counterelectrode is either negligible or is accommodated in a non-load
bearing manner. In this instance active materials are selected primarily
according to their elastic constants and strains.
In a second type, both the positive electrode and negative electrode are
load-bearing, and volume changes in both active materials in the
electrochemical couple (the positive electrode and the negative electrode)
are used, the net volume change of the electrochemical reaction being the
relevant quantity. Table 1 lists several electrochemical couples that use
carbon as the negative electrode material, from which it is seen that
several options give .about.5% volumetric strain in a cell where the
relative amounts of each material are adjusted to give a charge-balanced
cell. In both designs, other issues such as rate capability (bandwidth),
reversibility in cycling, and stability and safety over a wide range of
operating temperatures must also be considered in the selection process.
Using the materials of Table 2, it is also possible to design actuators
of a type that expands upon charging of the electrochemical cell, or one
that expands upon discharging. Table 1 provides four examples that expand
upon charging of the cell and one that expands upon discharging. As another
example of actuators that expand upon discharging, any electrode-active
compound that has a lithium insertion potential lower than that of the
"zero-strain" material Li.sub.4Ti.sub.5O.sub.12 (Table 2), and which
expands upon lithiation, will comprise the negative electrode when used
with Li.sub.4Ti.sub.5O.sub.12. Such a cell will spontaneously discharge
when electrons are allowed to flow between the electrodes, and lithium
will migrate from the Li.sub.4Ti.sub.5O.sub.12 to the other electrode,
causing it to expand. Having a cell that either expands or contracts upon
spontaneous discharge can be advantageous in designing the actuators of
the invention for applications where a particular "default" state is
desirable, for example in designing an actuated latch that defaults to
an open (or closed) state in the event of an intentional or accidental
short-circuit of the electrochemical actuator.
The stress that an actuator can be subjected to while producing useful
strain, or the "blocked stress" that can be produced by an actuator
undergoing zero or small strain, are important performance
characteristics that bear directly on the practical utility of the
actuator. In this respect, Table 2 and earlier discussion illustrates a
particular advantage of the electrochemical actuators of the invention,
which is the high elastic modulus of the active materials. In this
invention we recognize and design actuators to utilize the fact that
electrochemically-induced strains are substantial, and at the same time
many ion-storage compounds including graphite, metal alloys, and
intercalation oxides have high elastic modulus (50-150 GPa), more than
a thousand times greater than other actuator materials such as
electroactive polymers or gels, thereby providing for large actuation
authority as well as large strain.
In addition to high actuation energy density and actuation stress, one
measure of actuation authority that permits comparisons with
piezoelectric actuator technology is the coefficient e.sup.33, which
refers to actuation stress generated per unit electric field (Units:
Pa/V/m=C/m.sup.2). (In the case of piezoelectrics, this coefficient is
maximized for stresses in the direction of the applied electric fields,
signified by the superscript "33."). Consider a laminated electrochemical
actuator having cathode and anode thicknesses comparable to those in
current lithium ion battery technology, as schematized in FIG. 37. As an
example such a device may have an intercalation compound as one electrode,
a stiff but porous ceramic separator, and an inorganic negative electrode
of high elastic modulus, as shown in FIG. 38. For a 200 micrometer thick
layer (typical for battery electrodes) of the electrochemical insertion
compound in FIG. 1, when formulated as a powder-based composite electrode,
will have a Young's modulus of Y=50 GPa (assumed to be reduced from the
single crystal value of .about.150 GPa). Under 3.3V applied voltage this
electrode can be fully intercalated to reach a linear strain
of .epsilon..about.1.5%, thereby generating e.sup.33=3.8.times.10.sup.4
C/m.sup.2. This value considerably exceeds the e.sup.33 values obtained
with the best-known piezoelectrics, of 15-40 C/m.sup.2. The corresponding
actuation specific energy, taken as 1/2Y.epsilon..sup.2/.rho., the
strain energy density, taken as 1/2Y.epsilon..sup.2/.rho. where .rho. is
the material density, is about 2050 J/kg (5.6.times.10.sup.3 kJ/m.sup.3)
for the active material layer, and .about.1000 J/kg (2.8.times.10.sup.3
kJ/m.sup.3) for an actuator stack containing one-half by weight or volume
of inactive supporting layers. These values also greatly exceed typical
values of 13.5 J/kg and 100 kJ/m.sup.3 for a PZT piezoelectric ceramic.
At a stack volumetric strain energy density of 2.8.times.10.sup.3
kJ/m.sup.3, and 1.5% linear strain, the equivalent blocked stress
is .about.375 MPa. These comparisons illustrate the advantages of the
present invention over existing actuation technology where high actuation
energy, high actuation authority, and large strain is required, and their
usefulness in a wide variety of adaptive structures requiring significant
strain coupled with high authority.
Since batteries are energy storage devices, the total amount of stored
electrical energy is naturally maximized; typical stored energy levels
for unpackaged rechargeable lithium ion batteries (i.e., the active
"stack" alone without the can) are 550 Wh/liter and 200 Wh/kg. In such
cases, and even in electrochemical actuators of the invention designed
without regard to electrical energy storage and operating at less than
1V or even less than 0.5V applied voltage, during a charge/discharge cycle
the mechanical work done may be only a few percent of the total electrical
energy stored. This low level of electromechanical coupling is largely
responsible for the high blocked stresses that are achievable, i.e.
discharging a charged battery through the application of an external
stress is difficult. In one embodiment, the actuator is designed such that
the electrical energy is shuttled from the actuator to a storage battery,
or in another embodiment, between two actuators acting in concert so that
as one is charged the other is discharged, and the positive and negative
strains simultaneously produced add to produce a desired deformation. In
one embodiment, the invention allows for the use of antagonistic actuators
so that as one is charged, another is discharged, having both act
beneficially from the point of view of strain while shuttling the
electrical energy between the two so that it is not resistively dissipated.
Thus, according to this aspect of the invention, the losses in the system
may be primarily the low resistive losses that are produced as the charge
is shuttled between actuators.
In one embodiment, the intercalated material refers to an ion insertion
compound, and in one embodiment, a solid-state ion insertion compound such
as is used in battery systems, which is intercalated within the structure
of the actuator, as described herein. In another embodiment, the
intercalating species is a proton or an alkali metal or an alkaline earth
metal. In one embodiment, the alkali metal is lithium.
In another embodiment, the high-modulus inorganic compounds are
exemplified by the lithium transition metal oxide positive electrodes
(e.g., LiCoO.sub.2, LiMn.sub.2O.sub.4, LiNiO.sub.2, LiFePO.sub.4) and
carbon negative electrodes developed as storage electrodes for
rechargeable battery systems. These, and in other embodiments, other
similar compounds can be intercalated with Li+ ions at low voltages of
1.5-5V to produce large and reversible volume changes of, in some
embodiments, 3-13%.
In another embodiment, the ion insertion mechanisms may make use of an
alloying of lithium with various metals and metalloids, such as, for
example, Sn, or Si, which, in another embodiment may result in volume
expansions in excess of 250%.
In one embodiment, the electrochemically-induced strain produced for
actuation, when using intercalation compounds, which are oxides of high
elastic modulus (50-150 GPa) will allow large actuation authority as well
as large free strain, such that stresses can be produced approaching the
intrinsic compressive strength of the materials. Furthermore, these
compounds have low densities (3.5-5 g/cm3) compared to lead-based
piezoelectrics or metal alloys comprising magnetostrictors and shape
memory alloys.
In one embodiment, packaged actuators of this invention may have densities
of 2-4 g/cm.sup.3, which can produce high actuation authority, suitable
for a broad range of applications.
In one embodiment, the volumetric or dimensional change in said actuator
may range from 0.1-300%. In one embodiment, the volumetric or dimensional
change in said actuator may range from 0.1-10%, or in another embodiment,
the volumetric or dimensional change in said actuator may range from
0.1-50%, or in another embodiment, the volumetric or dimensional change
in said actuator may range from 0.1-100%, or in another embodiment, the
volumetric or dimensional change in said actuator may range from 1-100%,
or in another embodiment, the volumetric or dimensional change in said
actuator may range from 10-100%, or in another embodiment, the volumetric
or dimensional change in said actuator may range from 1-200%, or in another
embodiment, the volumetric or dimensional change in said actuator may
range from 10-200%, or in another embodiment, the volumetric or
dimensional change in said actuator may range from 50-200%, or in another
embodiment, the volumetric or dimensional change in said actuator may
range from 100-200%, or in another embodiment, the volumetric or
dimensional change in said actuator may range from 10-300%, or in another
embodiment, the volumetric or dimensional change in said actuator may
range from 100-300%, or in another embodiment, the volumetric or
dimensional change in said actuator may range from 50-300%. In another
embodiment, the volumetric or dimensional change in an actuator of this
invention may be reversible.
In one embodiment, the volumetric or dimensional change in said actuator
may be a function of the current flow induced by an applied voltage. In
one embodiment, the electrochemical actuator may be subjected to a varying
voltage. In one embodiment, increasing the voltage or current over time
may result in a gradual increase in volume. In another embodiment,
decreasing voltage or current over time results in a gradual decrease in
volume, or in another embodiment, in a gradual increase in volume. In
another embodiment, cycles of varied voltage may be desired in order to
induce discreet changes in volume.
In another embodiment, an electrode of an actuator of this invention is
initially enriched in, and may serve as a source for, the intercalating
species. In another embodiment, a negative electrode of an actuator of
this invention may serve as a source for the intercalating species. In
another embodiment, a positive electrode of an actuator of this invention
may serve as a source for the intercalating species.
In another embodiment, the electrode comprises a high elastic modulus
compound. In another embodiment, an electrode comprises an ion transition
metal oxide. In another embodiment, the ion transition metal oxide is a
proton or an alkali metal or an alkaline earth metal. In another embodiment,
the alkali metal is lithium. In another embodiment, an electrode comprises:
LiCoO.sub.2, LiFePO.sub.4, LiNiO.sub.2, LiMn.sub.2O.sub.4, LiMnO.sub.2,
LiMnPO.sub.4, Li.sub.4Ti.sub.5O.sub.12, and their modified compositions
and solid solutions. In another embodiment, an electrode comprises: an
oxide compound comprising one or more of titanium oxide, vanadium oxide,
tin oxide, antimony oxide, cobalt oxide, nickel oxide or iron oxide. In
another embodiment an electrode comprises TiSi.sub.2, MoSi.sub.2,
WSi.sub.2, and their modified compositions and solid solutions. In
another embodiment an electrode comprises a metal or intermetallic
compound. In another embodiment an electrode is lithium or a lithium-metal
alloy, which may be crystalline, nanocrystalline, or amorphous. In
another embodiment the negative electrode is one or more of aluminum,
silver, gold, boron, bismuth, gallium, germanium, indium, lead, antimony,
silicon, or tin. In another embodiment, an electrode is carbon in the form
of graphite, a carbon fiber structure, a glassy carbon structure, a highly
oriented pyrolytic graphite, a disordered carbon structure or a
combination thereof. In another embodiment, the intercalating species is
an ion. In another embodiment, a proton or an alkali metal or an alkaline
earth metal.
In another embodiment, the positive or negative electrode compounds
exhibit an elastic modulus ranging between 10-500 GPa. In another
embodiment, the compound exhibits an elastic modulus ranging between
50-150 GPa, or in another embodiment, the compound exhibits an elastic
modulus ranging between 50-350 GPa, or in another embodiment, the compound
exhibits an elastic modulus ranging between 50-450 GPa, or in another
embodiment, the compound exhibits an elastic modulus ranging between
10-250 GPa, or in another embodiment, the compound exhibits an elastic
modulus ranging between 10-350 GPa, or in another embodiment, the compound
exhibits an elastic modulus ranging between 10-450 GPa, or in another
embodiment, the compound exhibits an elastic modulus ranging between
25-250 GPa, or in another embodiment, the compound exhibits an elastic
modulus ranging between 25-500 GPa, or in another embodiment, the compound
exhibits an elastic modulus ranging between 50-500 GPa, or in another
embodiment, the compound exhibits an elastic modulus ranging between
50-300 GPa.
In another embodiment, an electrode comprises an ion transition metal
oxide. In another embodiment, said ion transition metal oxide is a proton,
alkali metal, or alkaline earth metal. In another embodiment, the alkali
metal is lithium. In another embodiment, an electrode comprises:
LiCoO.sub.2, LiFePO.sub.4, LiNiO.sub.2, LiMn.sub.2O.sub.4, LiMnPO.sub.4,
Li.sub.4Ti.sub.5O.sub.12, or their modified compositions or solid
solutions. In another embodiment, the intercalating species is an ion.
In another embodiment, a proton or an alkali metal or an alkaline earth
metal.
In one embodiment, the electrochemical actuators of this invention have
a negative electrode or positive electrode, or combination thereof,
comprising a single crystal or, in another embodiment, a polycrystal
having preferred crystallographic orientation of its crystallites. In
another embodiment, the electrochemical actuators of this invention have
a negative electrode or positive electrode, or combination thereof,
comprising a multiplicity of individual crystallites or a powder. In
another embodiment, the multiplicity of individual crystallites or a
powder, wherein there is a preferred crystallographic orientation of the
crystallites or powder particles. In another embodiment, the
electrochemical actuators of this invention have a negative electrode or
positive electrode, or combination thereof, comprising a multiplicity of
particles of an amorphous or disordered material.
In another embodiment, an actuator of this invention further comprises
a current collector, which, in another embodiment, comprises a conductive
material. In another embodiment, an actuator of this invention further
comprises a separator that is electronically insulating, which in one
embodiment is porous, or in another embodiment, is rigid. In one
embodiment, the porous separator comprises a microporous polymer. In
another embodiment, the porous separator comprises a porous
electronically insulating ceramic material, which in another embodiment,
is alumina, an aluminosilicate, cordierite, or a silicate glass. In
another embodiment, the electrodes of an actuator of this invention
further comprise a conductive additive.
In another embodiment, an actuator of this invention further comprises
an electrolyte. In one embodiment, the electrolyte is a solid electrolyte,
or in another embodiment, the electrolyte is a liquid or gel electrolyte.
In another embodiment, an actuator of this invention further comprises
an external packaging layer, which may be, in one embodiment, an
electrochemically-insulating layer, or, in another embodiment, a
protective layer or, in another embodiment, a combination thereof.
In one embodiment of the invention, intercalation of the species in an
actuator of this invention can occur upon both application of the voltage
and cessation thereof. In one embodiment, the applied voltage is in a range
of between 0.1-15 V. In another embodiment, the applied voltage is in a
range of between 1-5V. In another embodiment, the applied voltage is in
a range of between 0.1-5 V. In another embodiment, the applied voltage
is in a range of between 1-10 V. In another embodiment, the applied voltage
is in a range of between 1-15 V. In another embodiment, the applied voltage
is in a range of between 5-15 V. In another embodiment, the applied voltage
is in a range of between 5-10 V. In another embodiment, the applied voltage
may be varied, which may, in another embodiment, influence the amount of
intercalation, and in another embodiment, the degree of volume change.
In another embodiment, the volumetric or dimensional change in an actuator
of this invention is in the negative electrode or positive electrode or
a combination thereof. In another embodiment, the volumetric or
dimensional change is reversible. In another embodiment, intercalation
in an actuator of this invention produces high strain.
In one embodiment, the strain produced ranges from 0.1% to 300%, or in
another embodiment, the strain produced ranges from 1% to 300%, or in
another embodiment, the strain produced ranges from 10% to 300%, or in
another embodiment, the strain produced ranges from 0.1% to 200%, or in
another embodiment, the strain produced ranges from 10% to 300%, or in
another embodiment, the strain produced ranges from 10% to 200%, or in
another embodiment, the strain produced ranges from 50% to 300%, or in
another embodiment, the strain produced ranges from 50% to 200%.
In another embodiment, a negative electrode, or in another embodiment,
a positive electrode, in an actuator of this invention serves as a donor
or acceptor or combination thereof of an intercalating species.
The electrochemical actuators of the invention may have many different
constructions or designs or architectures. In some embodiments they may
be implemented with constructions similar to storage batteries. In one
embodiment, in a form similar to a thin-film battery, as schematically
depicted in FIG. 37. The actuator 24 may be positioned on a substrate 26.
The actuator comprises a negative electrode 28, and a positive electrode
30, which is separated from the negative electrode by an electrolyte layer
32. In one embodiment, the electrolyte is a solid electrolyte, or in
another embodiment, a liquid electrolyte. Current collectors for the
negative electrode 34 and positive electrode 36 may also be provided. A
protective coating 38 may be present as well, which may comprise an
insulating material.
In other embodiments, the actuator may have a design that is similar to
multilayered storage batteries of either stacked or wound designs or
hybrids thereof, including for example designs where a separator film is
continuously wound around a series of sequentially stacked discrete
electrodes. Such designs are well-known to those skilled in the art of
batteries. In one embodiment, the invention provides a Multilayer Stacked
Electrochemical Actuator, comprising two or more negative electrode
layers, two or more positive electrode layers, and an intercalating
species, wherein the Multilayer Stacked Electrochemical Actuator is
subjected to an applied voltage, whereby application of the voltage or
cessation thereof induces intercalation of the intercalating species in
the actuator, resulting in a volumetric or dimensional change of the
actuator.
Electrodes may be fabricated for the actuators of the invention by methods
similar to those used for storage batteries. In one embodiment, according
to this aspect of the invention, the active materials may be cast from
powder-based suspensions containing a polymer binder and conductive
additive such as, in one embodiment, carbon, then calendered (rolled)
under high pressure (for example, several tons per linear inch) to densely
compacted layers in which the volume percentage of active material is
between 50 and 70%.
In one or more embodiments, a multilayer stacked or wound electrochemical
actuator may use a porous polymer separator film similar to those used
in storage batteries.
As exemplified herein, multilayer electrochemical actuators of this
invention that use a construction similar to those of storage batteries,
in particular having electrodes containing polymer binder and liquid or
gel electrolyte, having a porous polymer separator that is load bearing
during the function of the actuator, or having external packaging that
comprises relatively low modulus polymer materials, will, in some
embodiments, have a soft construction compared to other actuators of the
invention, due to the low modulus materials used and/or excess internal
volume in the multilayer actuator. Under mechanical load, such actuators
may exhibit, in some embodiments, plastic deformation or viscous creep
or viscoelastic deformation. In order to obtain useful mechanical work
from such actuators, according to one aspect of the invention,
electrochemical actuators of such design may be mechanically pretreated
or processed so as to provide greater stiffness, higher actuation energy
density, higher actuation strain, decreased creep deformation, lower
hysteresis of strain, improved reversibility of actuation performance
over multiple actuation cycles, or a combination thereof. In one
embodiment, a multilayer actuator is subjected to a hydrostatic pressure
to consolidate the actuator, remove free volume, and improve performance.
In another embodiment, a uniaxial stress is applied to the multilayer
actuator normal to the layers to remove excess internal volume, to
consolidate the stack, increase the stiffness of the actuator, or to
remove creep deformation. Such applied stresses of hydrostatic or
nonhydrostatic nature cannot typically be increased without limit, as
internal shorting of the electrode layers or current collectors or tabs
may occur. Even at stresses not sufficient to cause internal short
circuits, microporous polymer separators or particle-based electrodes
may be consolidated to an extent that inhibits the function of the actuator.
However, surprisingly it was found as exemplified herein, that a very high
preconditioning pressure may be applied to a multistack actuator to
improve its performance without causing internal failure.
Thus in some embodiments, a uniaxial or hydrostatic pressure is used for
preconditioning of an assembled laminated actuator. In some embodiments,
the applied pressure may be as high as 10,000 psi (69 MPa), in other
embodiments as high as 20,000 psi (138 MPa) or as high as 30,000 psi (207
MPa), or even as high as 45,000 psi (310 MPa), without causing internal
failure and improving the performance of the actuator thereafter.
In other embodiments of laminated electrochemical actuators
incorporating a microporous polymer separator layer between active
material electrodes, high mechanical energy densities and high strains
are obtained under substantial applied stresses. As illustrated by the
Examples, in some embodiments such multilayer stacked actuators are used
to provide actuation strains from 0.5% to 5% under stresses from 0.1 MPa
to 50 MPa and provide actuation energy densities from 1 to 400 kJ/m.sup.3.
For one exemplary actuator and conditions of operation, 4% strain is
obtained while actuating under 1 MPa stress, providing 40 kJ/m.sup.3
energy density, and 2.5% strain is obtained while actuating under 10 MPa
stress, providing 250 kJ/m.sup.3 energy density. In other Examples and
embodiments lower strains and associated stresses and energy densities
are obtained that provide the ability to conduct useful mechanical work.
In some embodiments an actuator of the invention provides high actuation
speed. In some embodiments, an actuator of similar construction to a high
charge and discharge rate battery is provided, in which substantially
complete charging or discharging of the cell is possible in less than 6
minutes (10 C rate of charging or discharging), or less than 4 min (15
C rate), or less than 3 min (20 C rate). In other such embodiments, ion
storage (faradaic) electrode materials are known that are capable of
substantially complete charge and discharge in as short as 18 sec (200
C rate), allowing a comparable rate of actuation in an electrochemical
actuator using such materials. In some embodiments, the rate of actuation
is increased by charging or discharging over times that permit only a
portion of the total or reversible charge capacity of the actuator to be
reached.
As illustrated by the Examples, in some embodiments greater than 1.5%
under an applied stress greater than 0.5 MPa, greater than 1.5% as high
as 4% under stresses as high as 5 MPa, or as high as 2.5% under stresses
as high as 20 MPa, providing for actuation energy densities as high as
400 kJ/m.sup.3. In some embodiments, uniaxial stresses as high as 5 MPa,
10 MPa or even 20 MPa may be applied while conducting actuation without
significant loss of actuation energy density or actuation strain or rate
of actuation.
In other embodiments, when designing some of the electrochemical
actuators of the invention, use of materials including separators that
have a high elastic modulus, and are capable of withstanding high applied
loads without loss of function are employed. Thus the Multilayer Stacked
Electrochemical Actuator 40 may be implemented, in one embodiment, as
schematically depicted in FIG. 38. According to this aspect, in one
embodiment, the active layer is the positive electrode layer 42, which
comprises a thick layer, which in one embodiment may also comprise a binder.
An electronically-insulating, separator layer 44 may, in another
embodiment, be constructed of a high stiffness porous ceramic, such as
a silicate based ceramic, or in this case a porous Al.sub.2O.sub.3, as
illustrated in FIG. 38. The counter-electrode 46 may be embedded in the
porous separator so that it is not load-bearing, in this case, Li embedded
in the porous Al.sub.2O.sub.3. Liquid electrolyte may be infiltrated in
the actuator 48. In FIG. 38, 44 is a porous Al.sub.2O.sub.3 structural
separator, 46 is Li (non load-bearing) in porous Al.sub.2O.sub.3
insulator, 48 is liquid electrolyte infiltrated, 52 is a power source,
and 54 is a 1 cm.sup.3 stacked actuator.
In another embodiment, a high stiffness separator comprises a layer of
electronically insulating particles, such as particles of an insulating
ceramic material. Said layer has greater mechanical flexibility while
maintaining porosity under high actuation loads. In one embodiment the
porous particulate separator is cast as a particulate or slurry layer on
the mating surfaces of one or both electrodes prior to assembly of the
layers, using methods well-known to those skilled in the art of ceramic
processing or coating technology such as spray deposition, doctor blade
coating, screen printing, web coating, comma-reverse coating, or slot-die
coating. In one embodiment the particulate separator comprises particles
of glass, a silicate ceramic, aluminum oxide, aluminosilicates, or other
mixed-metal oxides or nitrides or carbides that are electronically
insulating.
In another embodiment, the counter electrode 46 may be replaced by an
intercalation compound-embedded within a rigid separator, or in another
embodiment, by a layer that is mechanically functional. Such
substitutions may be utilized in a stacked actuator design, 50. The power
source 52 may be connected to aluminum 38, and copper 52 current collectors,
respectively. A compact, unitized multilayer actuator 54, such as that
demonstrated in this embodiment, may be distributed in adaptive
structures in a variety of configurations to impart desired degrees of
freedom. In one embodiment, a device that can be prepared in a
reduced-volume state (i.e., by charging or discharging), then inserted
into a structure can be actuated in expansion. Such unitized actuators
could also be easily replaced, simplifying maintenance of an adaptive
structure.
The energy density of electrochemical actuators (ECAs) may be high, in
another embodiment, and the choice of materials will influence the
resulting energy densities obtained. The resulting volume changes may
range, in one embodiment, from 0.1 to 50%, or in another embodiment, from
0.1 to 1%, or in another embodiment, from 1 to 5%, or in another embodiment,
from 5 to 8%, or in another embodiment, from 5 to 10%, or in another
embodiment, from 8 to 10%, or in another embodiment, from 10 to 15%, or
in another embodiment, from 15 to 20%, or in another embodiment, from 5
to 15%, or in another embodiment, from 5 to 20%, or in another embodiment,
from 20 to 25%, or in another embodiment, from 10 to 20%, or in another
embodiment, from 10 to 25%, or in another embodiment, from 20 to 35%, or
in another embodiment, from 25 to 35%, or in another embodiment, from 15
to 35%, or in another embodiment, from 25 to 40%, or in another embodiment,
from 25 to 50%, or in another embodiment, from 35 to 40%, or in another
embodiment, from 35 to 50%.
The electrochemical actuators of this invention, allow for mechanical
energy production. In one embodiment, any electrochemical actuator of
this invention, including, for example a Multilayer Stacked Actuator of
this invention, allows for mechanical energy production, and can operate
under stress conditions. In one embodiment, the volumetric or dimensional
change occurs against an applied stress such that mechanical work is
conducted, where the mechanical work divided by the initial volume of the
actuator (mechanical energy density) exceeds (kJ/m3) values of between
0.1-5000 kJ/m.sup.3. In one embodiment, the mechanical energy density
exceeds 1 kJ/m.sup.3, or in another embodiment, the mechanical energy
density exceeds 10 kJ/m.sup.3, or in another embodiment, the mechanical
energy density exceeds 50 kJ/m.sup.3, or in another embodiment, the
mechanical energy density exceeds 100 kJ/m.sup.3, or in another
embodiment, the mechanical energy density exceeds 200 kJ/m.sup.3, or in
another embodiment, the mechanical energy density exceeds 300 kJ/m.sup.3,
or in another embodiment, the mechanical energy density exceeds 500
kJ/m.sup.3, or in another embodiment, the mechanical energy density
exceeds 1000 kJ/m.sup.3, or in another embodiment, the mechanical energy
density exceeds 1250 kJ/m.sup.3, or in another embodiment, the mechanical
energy density exceeds 1500 kJ/m.sup.3, or in another embodiment, the
mechanical energy density exceeds 1750 kJ/m.sup.3, or in another
embodiment, the mechanical energy density exceeds 2000 kJ/m.sup.3, or in
another embodiment, the mechanical energy density exceeds 2250 kJ/m.sup.3,
or in another embodiment, the mechanical energy density exceeds 2500
kJ/m.sup.3, or in another embodiment, the mechanical energy density
exceeds 2750 kJ/m.sup.3, or in another embodiment, the mechanical energy
density exceeds 3000 kJ/m.sup.3, or in another embodiment, the mechanical
energy density exceeds 3250 kJ/m.sup.3, or in another embodiment, the
mechanical energy density exceeds 3500 kJ/m.sup.3, or in another
embodiment, the mechanical energy density exceeds 3750 kJ/m.sup.3, or in
another embodiment, the mechanical energy density exceeds 4000 kJ/m.sup.3,
or in another embodiment, the mechanical energy density exceeds 4500
kJ/m.sup.3, or in another embodiment, the mechanical energy density
exceeds 5000 kJ/m.sup.3, or any range in between.
In another embodiment, the electrochemical actuators of this invention
have a volumetric or dimensional change occurring against an applied
stress, such that mechanical work is conducted, wherein the mechanical
work divided by the mass of the actuator (specific mechanical energy)
exceeds between 0.04-2,000 J/g. In one embodiment, the specific
mechanical energy exceeds 0.4 J/kg, or in another embodiment, the specific
mechanical energy exceeds 1 J/kg, or in another embodiment, the specific
mechanical energy exceeds 2 J/kg, or in another embodiment, the specific
mechanical energy exceeds 3 J/kg, or in another embodiment, the specific
mechanical energy exceeds 4 J/kg, or in another embodiment, the specific
mechanical energy exceeds 5 J/kg, or in another embodiment, the specific
mechanical energy exceeds 10 J/kg, or in another embodiment, the specific
mechanical energy exceeds 20 J/kg, or in another embodiment, the specific
mechanical energy exceeds 40 J/kg, or in another embodiment, the specific
mechanical energy exceeds 80 J/kg, or in another embodiment, the specific
mechanical energy exceeds 100 J/kg, or in another embodiment, the specific
mechanical energy exceeds 200 J/kg, or in another embodiment, the specific
mechanical energy exceeds 300 J/kg, or in another embodiment, the specific
mechanical energy exceeds 400 J/kg, or in another embodiment, the specific
mechanical energy exceeds 500 J/kg, or in another embodiment, the specific
mechanical energy exceeds 750 J/kg, or in another embodiment, the specific
mechanical energy exceeds 1000 J/kg, or in another embodiment, the
specific mechanical energy exceeds 1200 J/kg, or in another embodiment,
the specific mechanical energy exceeds 1350 J/kg, or in another embodiment,
the specific mechanical energy exceeds 1500 J/kg, or in another embodiment,
the specific mechanical energy exceeds 1600 J/kg, or in another embodiment,
the specific mechanical energy exceeds 1800 J/kg, or in another embodiment,
the specific mechanical energy exceeds 2000 J/kg.
The actuators of the invention have in some aspects designs or
architectures providing for improved load bearing, or for load bearing
by a single active material of the cell. Such designs can also avoid having
a porous separator under load as in the laminated designs. Thus in one
embodiment, an actuator of this invention may have an electrode compound
or composite electrode providing actuation forming a multiplicity of
load-bearing members in the primary direction or directions of actuation,
wherein each member is exposed to an intercalation compound in one or more
directions from the primary direction or directions of actuation. In
another embodiment, the members may be formed as a pattern of posts or
bars or ridges. In another embodiment, the actuator design comprises an
array of posts wherein only one active material is load-bearing. In
another embodiment, the actuator design is such that when one electrode
performs actuation, the other electrode is buried in a stiff porous
separator, such that it (the latter) is not load-bearing.
In another embodiment, the lateral dimensions of the members may have at
least one half-thickness that is sufficiently small to allow substantial
intercalation of the intercalation compound, during a desired time period
of actuation. In another embodiment, the intercalation compound source
is placed adjacent to a pattern of members or, in another embodiment,
between members allowing ion insertion from a direction that is not the
primary direction or directions of actuation.
In one embodiment, an electrochemical actuator of this invention will have
a high load-bearing and stress-generating capacity as well as a high rate
of actuation. The actuation compounds of the invention as well as
composite electrodes incorporating such actuation compounds are capable
of supporting substantial stress in tensile loading, in one embodiment,
and in another embodiment, even greater stress in compressive loading.
For example, a polycrystalline graphite material may have a compressive
failure stress of 100-200 MPa, a highly oriented or single crystal
graphite may have compressive failure stress in the c-axis direction
(normal to the graphene planes) in excess of 500 MPa or even in excess
of 1 GPa, and a densely sintered metal oxide intercalation compound may
have compressive failure strength in excess of 400 MPa or even in excess
of 1 GPa. In one embodiment, certain applications may require ion
insertion to occur from a direction other than the highly loaded
directions. For example, in the fiber actuators described herein, in one
embodiment, load bearing is primarily along the axis of the fibers, while
ion insertion occurs in the transverse direction.
According to this aspect of the invention, and in one embodiment,
actuators are designed to allow ion insertion from a transversely or
laterally placed ion source into load-bearing members of an actuator that
are supporting compressive or tensile load. The lateral or transverse
dimensions of the load-bearing members may be selected on the basis of
ion and electron transport kinetics well-known to those skilled in the
art of electrochemical materials and devices.
In one embodiment, where lithium intercalation compounds are used for
electrochemical actuation, the time necessary to lithiate or delithiate
a certain cross-section of material to a desired ion concentration and
corresponding strain may be readily determined knowing the rate of ion
transport into the material. Such determinations may be readily tested
experimentally or made theoretically using tabulated or estimated values
of properties such as ion diffusion coefficients, ionic and electronic
conductivities, and surface reaction rate coefficients.
Extremely high stresses and energy densities are achievable using a
suitably designed actuator and actuating material, as will be understood
by one skilled in the art, and as exemplified herein. In one embodiment,
an oriented graphite material is used as a load bearing actuating material,
with the c-axis of the graphite oriented substantially in the direction
of desired actuation. In one embodiment the graphite has a multiplicity
of individual elements together bearing the load, each of which has a
smallest cross-sectional width that is 200 micrometers or less, allowing
substantial ion intercalation over a useful actuation time. As shown in
the Examples, in one such embodiments an actuation strain of as high as
1.2% is obtained under a stress as high as 100 MPa (one metric ton per
cm.sup.2), providing an energy density of 1200 kJ/m.sup.3, or 4.3% is
obtained under a stress of 30 MPa, providing an energy density of 1290
kJ/m.sup.3. While these Examples demonstrate the capabilities of the
present invention for extremely high actuation energy density, it is
understood that useful mechanical work can be performed according to the
invention while employing much lower strains and actuation energies than
the ultimate capabilities of a particular actuator.
In another embodiment, the actuator design is such that one or, in another
embodiment, both of the materials forming the electrochemical couple,
namely the positive and negative electrode materials, may be load bearing
material. In some embodiments this is desirable because one of the
materials may expand when the cell is charged or discharged while the other
contracts. By having the load borne by one active material, a larger net
strain and mechanical energy density may be obtained than in the case where
the two materials are joined in series in the direction of loading, and
the net strain includes that in both materials. By placing the two active
materials in a parallel arrangement between the load-bearing surface of
the actuator rather than in series, in another embodiment, it is also
possible to design the actuator such that both materials contribute to
mechanical actuation, but in different proportions or even in different
directions (expansion versus contraction) as the state of charge varies.
In some applications of electrochemical actuators it is advantageous to
provide for rotary motion. In one embodiment, the invention provides a
Rotational Electrochemical Actuator, comprising rolled layers of an
negative electrode, a positive electrode and an intercalating species,
wherein the rolled layers assume a laminate configuration, and wherein
the Rotational Electrochemical Actuator is subjected to an applied
voltage, whereby application of the voltage produces intercalation of the
intercalating species in the actuator, resulting in a volumetric or
dimensional change of the actuator such that the rolled laminate
configuration winds or unwinds, and torque is produced.
The Rotational Electrochemical Actuator 56 would use, in one embodiment,
a design similar to that of the Multilayer Stacked Electrochemical
Actuator, comprising laminates of current collectors 58, which, in one
embodiment, comprise aluminum and copper, negative electrodes 60, which
in another embodiment, comprise carbon, positive electrodes 62, which in
another embodiment comprise an oxide, and a separator 64, which in another
embodiment, may comprise a polymer film (FIG. 39). In another embodiment,
a structural aluminum layer 66 is added, or in another embodiment, the
aluminum foil current collector is replaced with structural aluminum. In
another embodiment, the copper layer may be structural as well. In another
embodiment, the Rotational Electrochemical Actuator is infiltrated with
electrolyte 68. The actuator may be assembled as a spiral 70, around an
inner mandrel 72, and covered by an outer shell 74. When the system is
charged, a significant volume change (.about.5%) would occur, causing the
rolled actuator to unwind. The amount of rotary motion induced would be
proportional to the product of the volume change and the number of turns
in the spiral. As a result, a spiral actuator with, say, 20 layers, would
be capable of very high torques, and significant rotary motion.
In one embodiment, Rotational Electrochemical Actuator winds, or unwinds,
in response to application of voltage, or cessation thereof. In another
embodiment, when the rolled laminate configuration winds or unwinds,
rotary motion is produced. In another embodiment, the rotary motion ranges
from 1-360.degree.. In another embodiment, the rotary motion produces 1
or more rotations, which, in another embodiment, are complete or
incomplete. In another embodiment, the rotation is in a clockwise
direction or counter clockwise direction, or a combination thereof.
It is possible that shear strains may be produced in the lamination, as
a result of the construction of the Rotational Electrochemical Actuator.
In one embodiment, shear strain is mitigated by using a thick polymer
separation layer to allow shearing motions between structural layers. In
one embodiment, selection of the polymer layer includes that of a low shear
modulus in order to allow the shear, but high bulk modulus to ensure that
the actuation energy in not wasted in the compression of the polymer layer.
In another embodiment, the spiral may be constructed with an additional
elastomeric layer to achieve this result.
In some applications of the electrochemical actuators of the invention,
it is advantageous to provide for actuation in one or more directions
within a plane, or to have the actuator exert a tensile stress. In one
embodiment, the invention provides a Continuous Fiber Electrochemical
Actuator, comprising a fibrous negative electrode, a positive electrode
and an intercalating species wherein the Continuous Fiber Electrochemical
Actuator is subjected to an applied voltage, whereby application of the
voltage or its cessation induces intercalation of the intercalating
species in the actuator, resulting in a volumetric or dimensional change
of the actuator, such that said fibrous negative electrode undergoes
elongation. By "continuous fiber" it is understood that the fibers
comprising the active material have an aspect ratio of at least 10 to 1
and preferably greater than 20 to 1, and are load bearing along the axis
of the fibers. In one embodiment a majority of the fibers continuously
span an actuator device comprising at least a positive electrode and
negative electrode and electrolyte.
In one embodiment, the Continuous Fiber Electrochemical Actuator 76 is
comprised of a fiber composite system, similar to graphite fiber
composites, in which the active fibers form the negative electrode 78,
which, in one embodiment are carbon fibers, and undergo significant
elongation under intercalation. (FIG. 40). In one embodiment, disordered
carbon fibers are utilized, which, in another embodiment, expand
isotropically upon lithium intercalation. The fiber negative electrode
may be separated from the positive electrode 80, which in one embodiment,
is a lithium-source positive electrode, by a polymer or inorganic
separator 82, and a liquid or solid electrolyte layer 84. Current
collectors 86 and 88, respectively, may be connected to the power source
90 in the actuator.
In one embodiment, the carbon fibers are the primary structural layer,
and are anchored at each end to form a completed actuator. In one
embodiment, the Continuous Fiber Electrochemical Actuator can actuate in
tension as well as in compression.
In another embodiment, the actuator 92 is comprised of individual negative
electrode fibers 94, such as carbon, are coated with a ceramic or polymer
electrolyte 96 and a lithiated positive electrode 98, connected to a power
supply 100 as shown in FIG. 41. These fibers could then be used to form,
in one embodiment, an active fiber composite 102, which, in another
embodiment, uses a conventional matrix (such as epoxy), found, in another
embodiment, in graphite-reinforced plastic composites. Masking the ends
of the fibers during the coating process would produce step layers, as
shown in the figure, allows, in another embodiment, the electrical
connections to be applied to the ends of the fibers.
In another embodiment, the Continuous Fiber Electrochemical Actuator is
comprised of multiple coated fibers, which are utilized to form a fiber
composite. In another embodiment, the composite further comprises a
matrix, which, in another embodiment, is a polymer. In another embodiment,
the composite of the Continuous Fiber Electrochemical Actuator comprises
fiber ends, which are uncoated. In another embodiment, the uncoated ends
of the fibers enable electrical connections to be applied to the ends of
the fibers.
In another embodiment, the Continuous Fiber Electrochemical Actuator
primarily actuates in tension. For example, graphite can be lithiated up
to a composition LiC.sub.6 with an accompanying volume expansion of 13.1%,
and disordered (isotropic) carbons can be lithiated to still higher
concentrations and expansions. A carbon fiber can, according to this
aspect of the invention, exhibit axial displacement of about 5%, while
possessing a high elastic modulus (>500 GPa for commercially available
disordered-carbon fibers).
In another embodiment, the Continuous Fiber Electrochemical Actuator
comprises multiple layers, which, in another embodiment are assembled in
parallel or in perpendicular orientation. In another embodiment, the
perpendicular orientation allows positive and negative shearing
actuation of the actuator, which, in another embodiment, produces torque,
or, in another embodiment, produces rotation. In another embodiment, the
perpendicular orientation allows for charge transfer between layers when
low voltage is applied.
In another embodiment, the Continuous Fiber Electrochemical Actuator
comprising multiple layers, wherein a layer of carbon fibers is added with
orientation perpendicular to a first layer. According to this aspect, both
positive and negative shearing actuation results, producing an actuator
capable of twisting an object, such as, in one embodiment, a wing or in
another embodiment a blade in both positive and negative directions. In
another embodiment, such an orientation reduces the total power
requirements, by allowing charge to be transferred back and forth between
layers at a low voltage. In another embodiment, such an actuation system
might be capable of 3% elongation in the fiber direction. In another
embodiment, the Continuous Fiber Electrochemical Actuator can be
constructed as a pack, similar in form factor to active fiber composite
(AFC) packs based on piezoelectric fibers, which could be used to actuate
a blade or wing, producing significant actuated twist capability (See FIG.
41).
In one embodiment, the invention comprises actuators that can deamplify
strain, and thereby amplify stress. In one embodiment, depicted in FIG.
30, a woven actuator is provided in which a transverse (or
through-thickness) displacement of one or more electrochemical actuators
is converted into a longitudinal or in-plane displacement with a strain
deamplification factor that is determined by the respective dimensions
of the actuator. The design features, construction, and testing of this
actuator type is exemplified in Example 9. Such actuators are useful in
numerous applications including shape-morphing or beam-bending
applications where a relatively thin actuator, for example one
sufficiently thin to use in the skin or shell of a fuselage, rotor, wing,
watercraft hull, or land vehicle body is desired.
In one embodiment, the woven structure comprises metallic wires, or in
another embodiment, a composite material, or a combination thereof. In
one embodiment, the composite material comprises graphite fibers, or in
another embodiment, fiberglass fibers in a matrix. In one embodiment,
"matrix" refers to any matrix known in the art, and may comprise, for
example, an epoxy, or in another embodiment, two-part epoxies,
temperature cured epoxies, thermoplastics, etc. In one embodiment, a
rubberizing agent (see Crawley, E. F. and Ducharme, E. H. ASME,
International Gas Turbine Conference and Exhibition, 32nd, Anaheim,
Calif.; UNITED STATES; 31 May-4 Jun. 1987. 11 pp. 1987) may be used to
lower the matrix modulus, to increase the flexibility of the mechanism.
In another embodiment, the amplifying mechanism is a composite structure
formed not by interweaving fibers, but by fibers running roughly parallel
on the top and bottom sides of one of more electrochemical actuators, with
the fibers on opposite sides stitched or sewn together on the left and
right of each EC actuator.
The high strain of the present electrochemical actuators notwithstanding,
many applications benefit from an amplification of strain, which for
energy conservation necessitates a deamplification of stress. In another
embodiment, the invention comprises actuators that amplify strain. In one
specific embodiment, the actuation strain of an electrochemical actuator
element or series of actuator elements, here a stack of multilayer
actuator devices, is amplified by an assembly incorporating a lever and
a fulcrum that also serves as a flexure. In one embodiment the housing
for the actuating elements or the lever and fulcrum are formed from one
piece of material, for example from an electro-discharge machined piece
of a metal or from a formed single body of a polymer or reinforced polymer
composite, providing for a compact and economical design. Such actuators
may be used singly or multiply as positioners, latches, lifters, or to
change the shape of a structure. While actuators having a lever and fulcrum
powered by piezoelectric elements are known, for example the commercial
products manufactured by Physik Instrumente, the present actuators have
a much larger range of motion as shown in Example 8.
In another embodiment, this invention provides a method of actuation,
comprising the step of applying a voltage to an actuator of this invention,
comprising an negative electrode, a positive electrode and an
intercalating species, wherein applying voltage causes current flow
inducing intercalation of the intercalating species in the actuator,
whereby intercalation induces a volumetric or dimensional change of an
actuator of this invention. The amount of actuation is in one embodiment
controlled by controlling the voltage, and in another embodiment by
controlling the total amount of current flowing into the device.
It is to be understood that all the embodiments for the actuators of this
invention listed herein, are applicable to methods of actuation using the
same, and are to be considered as part of this invention.
In another embodiment, this invention provides a method of producing
torque or rotary motion in a structure or an apparatus comprising a
Rotational Electrochemical Actuator, comprising the step of applying
electric current to a Rotational Electrochemical Actuator comprising an
negative electrode, a positive electrode and an intercalating species,
wherein applying current induces intercalation of the intercalating
species in the actuator resulting in a volumetric or dimensional change
of the actuator such that said rolled laminate layers unwind, and torque
or rotary motion is produced.
In another embodiment, this invention provides a structure or apparatus
comprising an actuator of this invention. In one embodiment, the structure
or apparatus is adaptive. In another embodiment, the actuator is used as
an element to apply stress at a site on the structure or apparatus that
is distal to the actuator. In another embodiment, the structure or
apparatus amplifies the volumetric or dimensional change induced by the
actuator.
In one embodiment the adaptive structure or apparatus 104 comprises an
electrochemical actuator of this invention 106, mounted on its surface
108 (FIG. 42A).
In one embodiment, a structure such as a beam or plate or any structure
of a size ranging from the MEMS scale to, in another embodiment, a large
scale structure can be actuated with a surface mounted electrochemical
actuator of this invention. In one embodiment, the electrochemical
actuators of this invention are designed to produce in-plane deformation
or actuation stress. In one embodiment, the deformation produced via
planar thin film electrochemical actuators of this invention is normal
to the plane of the surface where the actuator is positioned. In one
embodiment, deformation in such an orientation is least constrained and
construction of the actuator or, in another embodiment, its integration
within a structure or apparatus is so designed as to produce a high stress
or deformation in the plane of the surface.
In one embodiment, the actuators of this invention may produce blocked
stresses of between 0.1-1000 MPa. In another embodiment, the actuators
of this invention may produce blocked stresses of between 0.1-10 Mpa, or,
in another embodiment, actuators of this invention may produce blocked
stresses of between 0.1-100 Mpa, or, in another embodiment, actuators of
this invention may produce blocked stresses of between 1-10 MPa, or, in
another embodiment, actuators of this invention may produce blocked
stresses of between 1-100 MPa, or, in another embodiment, actuators of
this invention may produce blocked stresses of between 1-1000 MPa, or,
in another embodiment, actuators of this invention may produce blocked
stresses of between 10-100 MPa, or, in another embodiment, actuators of
this invention may produce blocked stresses of between 10-1000 MPa, or,
in another embodiment, actuators of this invention may produce blocked
stresses of between 100-1000 MPa.
In one embodiment, multiple actuators are distributed in an apparatus.
In one embodiment, the distributed electrochemical actuator technology
of this invention is capable of imparting multiple degrees of freedom to
active structures comprising the actuators.
In one embodiment, integration of an actuator within a structure or
apparatus 110 is as schematically depicted in FIG. 42B. The
electrochemical actuator, or in another embodiment, actuators 140, are
in one embodiment, thin film, or in another embodiment, thick film
laminated electrochemical actuators, which are oriented normally to the
surface, and are positioned within a stiff surface layer 120, on a
substrate 130.
The positioning and design of the actuators may result in a greater
deformation produced in the surface plane, via, in one embodiment,
changing the aspect ratio of the expanding and contracting elements (FIG.
42C), the positive electrode 150 and negative electrode 160. Such a
construction as depicted in the figure produces a large, in-plane, net
deformation upon charging/discharging of the actuator, evident when
viewed looking down the plane of the surface (C), or in cross-section (D).
In another embodiment, the laminated electrochemical actuator itself
undergo deformation. In one embodiment, the deformation is a bending of
the actuator itself, as a result of expansion of one electrode concurrent
with contraction of another, during the same charge or discharge cycle.
For example, and in one embodiment, an negative electrode comprising
carbon will expand, as carbon expands when lithiated and a positive
electrode comprising LiCoO.sub.2 expands when delithiated, resulting in
a partial compensation of any deformation of the actuator comprising the
two.
In another embodiment, an actuator 170 comprising a carbon or lithium
negative electrode 200, which expands when lithiated, and a
LiMn.sub.2O.sub.4 or LiFePO.sub.4 positive electrode 190, which
contracts when de-lithiated, if bonded to a separator 180, will produce
a marked bend in the entire structure (FIG. 43A).
In another embodiment, a laminated electrochemical actuator of thin film
or thick film design of this invention, wherein a volume change in both
negative electrode and positive electrode is being utilized
simultaneously, will position electrodes yielding maximum expansion, in
one embodiment, the negative electrode, facing outward from a surface that
is intended to be deformed from lesser to greater convexity. In one
embodiment, an airfoil 210 would be designed to comprise actuators
assuming such a configuration. According to this aspect, the actuator
would be positioned, such that the negative electrode is facing outward
230, from the surface of the apparatus 220, such that following actuation,
a greater curvature outward occurs. In one embodiment, such a
configuration enables the device to be discharged in the relaxed state.
In another embodiment, electrochemical actuation may be performed using
a supporting material such as a substrate as the electro-active material
itself (FIG. 43C). According to this aspect of the invention, and in one
embodiment, the structure comprising the actuator 240, comprises a
silicon wafer 250 that can be lithiated from the surface 270, via the
lithium metal or lithiated oxide electrode as the lithium source, in order
to induce volumetric expansion hence bending. In one embodiment, other
metalloids, or, in another embodiment, metals (e.g. Al which lithiates
to LiAl) or, in another embodiment, oxides may be used similarly.
In another embodiment, a structure or apparatus 280 may be made to bend
around more than one axial direction, such as, in another embodiment, to
twist and curve concurrently, by having an array of electrochemical
actuators 300 on the surface of the structure or apparatus 290 and
actuating them non-uniformly in a prescribed manner (FIG. 44).
In one embodiment, the structure or apparatus will twist about the x-axis
and bend about the y-axis, if individual actuators are actuated
appropriately to produce this result. According to this aspect of the
invention, and in one embodiment, if there is a net expansion induced on
the surface, then the surface will bend, as a whole in response, and, in
another embodiment, if different degrees of bending are induced locally
as one progresses down the x-axis, then overall, there will be a twisting
along this axis.
In another embodiment, according to this aspect of the invention, the
structure or apparatus may comprise a series of small actuators so
designed as to produce an overall twist in the structure comprising the
actuators, wherein the structure may be quite large, and the twisting
exerted despite high frictional and other resistance forces exerted on
the structure. For example, and in one embodiment, a series of Multilayer
Stacked Electrochemical Actuators with an aspect ratio of, in one
embodiment, 1, or in another embodiment, 0.5, or in another embodiment,
2.0, or in another embodiment, 1.5, or in another embodiment, between 0.5
to 2, is placed on a substrate, at an angle to the leading edge of the
substrate. In one embodiment, the Multilayer Stacked Electrochemical
Actuator is in the shape of a cube, or in another embodiment, in the shape
of a cylinder. In another embodiment, the Multilayer Stacked
Electrochemical Actuators range in size between 0.5 to 10 cm, or in another
embodiment, between 0.5 to 5 cm, or in another embodiment, 1 to 3 cm.
In another embodiment, the substrate is a wing of an aircraft 330, and
the actuators of this invention 320 arranged according to this aspect of
the invention are used to twist the wing (FIG. 45). In another embodiment,
the actuators may be utilized to raise and lower flaps positioned on a
wing, for greater flight control. In another embodiment, the actuators
of this invention may be utilized to reversibly unfurl a wing (FIG. 44B).
According to this aspect of the invention, and in other embodiments, the
actuators may be utilized for unfurling a fin or wing on a missile or
aircraft. In one embodiment, large strains produced by electrochemical
actuation enable the morphing of surfaces. By the term "morphing", it is
meant, in one embodiment, to refer to an overall change in structure. In
one embodiment, an otherwise rigid wing or fin may be furled when the
vehicle is stored, and unfurled when the vehicle is deployed, via the
electrochemical actuators of this invention. In another embodiment,
significant change in wing sweep is achieved, which, in another embodiment,
enables a vehicle comprising the electrochemical actuators of this
invention to have both subsonic and supersonic capabilities.
In one embodiment, the structure or apparatus moves in or beyond the
atmosphere. In one embodiment, such a structure or apparatus may be an
aircraft, a missile, a spacecraft or a satellite. In another embodiment,
such a structure or apparatus may be part of an aircraft, a missile, a
spacecraft, a worm, a robot or a satellite. In other embodiments, the part
may be a wing, a blade, a canard, a fuselage, a tail, an aileron, a rudder,
an elevator, a flap, a pipe, a propellor, a mirror, an optical element,
or a combination thereof. In other embodiments, the part may be an engine,
a motor, a valve, a regulator, a pump, a flow control device, a rotor,
or a combination thereof.
In another embodiment, the structure or apparatus moves in water. In one
embodiment, such a structure or apparatus may be a boat, a ship, a
submarine or a torpedo. In another embodiment, the structure or apparatus
is a part of a boat, a ship, a submarine or a torpedo. In another embodiment,
the part is a blade, a rudder, a pipe, a propellor, an optical element,
or a combination thereof. In another embodiment, the part is an engine,
a motor, a valve, a regulator, a pump, a flow control device, a rotor,
a switch or a combination thereof.
In another embodiment, the structure or apparatus is a bomb, a means of
transportation, an imaging device, a robotic, a worm, a prosthesis, an
exoskeleton, an implant, a stent, a valve, an artificial organ, an in vivo
delivery system, or a means of in vivo signal propagation.
For example, and in an embodiment of this invention, high-authority
control of helicopter rotor blades may be accomplished via the use of an
actuator of this invention. The actuators of this invention may be
utilized, in one embodiment of the invention, for producing
high-authority, low-bandwidth control required to allow auto-rotation,
or to improve hover performance at hover levels in aircraft. In one
embodiment, a Rotational Electrochemical Actuator of this invention will
produce a 10 degree tip rotation, or more, which may be used in hover
applications, which typically require 8-15 degrees of authority. In
another embodiment, a Rotational Electrochemical Actuator of this
invention will provide an electric, swashplateless rotor for use in hover
application.
In another embodiment, single bi-layer or stack actuators comprising a
rigid porous separator, or a solid electrolyte can be used, which provides
high stiffness to the actuator. A series of such actuator elements may
be patterned on a substrate, including on silicon glass, or aluminium
oxide, or some other such substrate of high stiffness, and used for high
force actuation, for production of a nastic structure. In one embodiment,
the term nastic structure refers to a structure, which deforms in response
to a stimulus. According to this aspect of the invention, a series of
actuators may be placed on a substrate which when activated, creates a
deformation, in another embodiment, in an overall structure comprising
the actuators.
In one embodiment, devices that utilize the technology of this invention
comprise motors, such as, in one embodiment, a linear, or, in another
embodiment, a rotational motor. In another embodiment, the device is a
pump, such as, in another embodiment, a microhydraulic pump, or in another
embodiment, a microfluidic pump. In another embodiment, the device is a
mirror array, or in another embodiment, an optical element used for
optical switching. In another embodiment, the device is a photonic device
where actuation induces a change in an optical path or properties. In
another embodiment, the device is a worm or robot that moves as a result
of actuation, moving, in another embodiment, a series of elements in a
given sequence.
The energy density of electrochemical actuators (ECAs) may be quite high,
and the choice of materials will influence the resulting energy densities
obtained, with, in another embodiment, the advantage of easier
distribution of ECAs throughout a morphing aircraft structure, or, in
another embodiment, their production as small units that can be ganged
to produce high authority at a single point or distributed widely over
a structure to produce localized control. In another embodiment, a
structure comprising the ECAs may be able to "morph" in many degrees of
freedom, and achieve high performance over a wide range of conditions.
In one embodiment, such an application is exploited in constructing parts
of an airplane. For example, in one embodiment, one might develop a wing
with distributed ECAs that would allow high levels of twist (5 deg or more)
which allow the elimination of ailerons, or, in another embodiment,
significant sweep changes (20 deg or more) to allow good performance at
both subsonic and supersonic speeds, or, in another embodiment, airfoil
shape changes (camber and thickness) large enough to optimize wing
performance over Mach numbers ranging from low subsonic to supersonic
speeds.
In another embodiment, this invention provides a pump comprising at least
one electrochemical actuator, comprising an negative electrode, a
positive electrode, an intercalating species, and at least one valve,
wherein following application of a voltage causing current flow in the
actuator, intercalation of the intercalating species produces a change
in volume in the actuator, such that fluid is directed through the valve.
In one embodiment, the pump comprises a series of actuators. In another
embodiment, the actuators may be placed in a parallel series. In another
embodiment, the actuators may be placed in a plane of a surface so as to
direct fluid through designed channels.
In one embodiment, a microfluidic pump may be designed, using an
electrochemical actuator of this invention, wherein the actuator produces
a net volume charge upon charging and discharging (FIG. 46). According
to this aspect of the invention, and in one embodiment, the microfluidic
pump 340, comprises a positive electrode 350, and negative electrode 360,
separated by an electrolyte layer 370, which according to this aspect of
the invention is a liquid electrolyte. In one embodiment, the electrolyte
may itself be the working fluid of the pump, or in another embodiment,
the working fluid may be a separate fluid from the electrochemical
actuator system. In another embodiment, the actuator undergoes a net
volume change upon charging and discharging, following the application
of voltage 390, or its cessation, respectively, which enables fluid
propulsion through the valves 380.
Volume changes that may be achieved, such as those exemplified in Example
3 herein, may range, in one embodiment, from 1 to 10%, or, in another
embodiment, from 5 to 10%, or, in another embodiment, from 10 to 15%, or,
in another embodiment, from 15 to 20%, or, in another embodiment, from
5 to 10%, or, in another embodiment, from 5 to 10%, or, in another
embodiment, from 20 to 25%, or, in another embodiment, from 25 to 30%,
or, in another embodiment, from 30 to 35%, or, in another embodiment, from
35 to 40%, or, in another embodiment, from 40 to 45%, or, in another
embodiment, from 45 to 50%, or any range as described herein.
In one embodiment, an assembly of actuators can be used to create a fluid
or gas pump or a microfluidic device. In one embodiment, a series of
actuators may be assembled in a plane, wherein actuation produces a net
flow of fluid though channels, whose shape is controlled by the actuator
design and positioning within the plane (FIG. 46B). In one embodiment,
the pump or microfluidic device 400 comprises a series of actuators 410,
which upon charging and discharging induce volume changes, which can, in
one embodiment, direct fluid flow from intake 420, through exit 420 of
the device, through channels whose shape may be controlled, in another
embodiment, via specific actuator design, which may comprise assembly on
a substrate 430. In one embodiment, operation of the actuators in a series
propels the fluid through the device. In another embodiment, positioning
of the actuators is such that channels are designed, as depicted in FIG.
46C. Such actuators can be, in one embodiment, of single bi-layer, or,
in another embodiment, of stacked design. In one embodiment, the device
will comprise a high molecule stack for the actuators. According to this
aspect of the invention, and in one embodiment, a rigid porous separator
or, in another embodiment, a solid electrolyte can be used, such as, in
another embodiment, a LIPON electrolyte. In another embodiment, the
stacked actuators may comprise thin film batteries in an array on a
substrate, in a single bi-layer (single electrochemical cell) or
multilayer stack sequence. In one embodiment, the substrate on which the
actuators are patterned may comprise silicon glass, aluminium oxide, or
any substrate of high stiffness, and may, in another embodiment, be used
for high force actuation, or, in another embodiment, in microfluidic
devices for fluid propulsion. In another embodiment, according to this
aspect of the invention, a nastic structure is thus designed, in which
a series of gas or liquid filled chambers are actuated so as to create
deformation of the overall structure.
In another embodiment, actuation is via a fluidic system, which comprises
an electrolytic membrane, which pumps an ion from one side to another,
producing a liquid rather than a gas in the process, as exemplified herein
in Example 4 and FIG. 15. By pumping a liquid, much higher actuation forces
can be produced since liquids have much lower compressibility. Actuators
of this kind can be used, in one embodiment, in fluidic, or in another
embodiment, in micro fluidic devices, or, in another embodiment, in micro
hydraulic devices, or in another embodiment, in nastic structures or, in
another embodiment, in compressing cellular micro-fluidic or, in another
embodiment, in micro hydraulic devices.
In one embodiment, such an electrochemical actuator, will comprise an
negative electrode, a positive electrode and an electrolytic membrane and
an ion, wherein application of voltage to the electrochemical actuator
or its cessation induces pumping of the ion from one side of the membrane
to the other side, resulting in the generation of a liquid, thereby
producing a volumetric or dimensional change in the actuator. In one
embodiment, the ion is a proton (H+). In another embodiment, the liquid
comprises H.sub.2O.sub.2, or in another embodiment, the liquid comprises
H.sub.2O.
In another embodiment, this invention provides a morphing plate, or in
another embodiment, morphing beam architecture comprising the actuators
of this invention. According to this aspect of the invention, and in one
embodiment, a plate architecture containing distributed electrochemical
actuators is provided, which may yield, in another embodiment, a multiple
shape target (FIG. 47). In one embodiment, the plate may comprise three
orientations of in-plane, independently-addressable actuators, such as,
for example, 0.degree., +60.degree., -60.degree., as illustrated by the
red-green-blue motif in FIG. 48A. This hexagonal network does not
necessarily represent actual physical cell walls or boundaries (although
such an assembly represents one embodiment of this invention), but may,
in another embodiment, describe a distribution of "unit cells", each acted
upon by a single actuator of a given orientation. Many degrees of morphing
freedom are possible in a plate, in another embodiment, as schematized
in FIG. 48B, in which the surfaces contain such arrays of embedded
addressable actuators.
In one embodiment, the construction in FIG. 48B may, for example, be a
10.times.10 array of actuators embedded in each side of a monolithic plate
made of a polymer or structural metal, or a composite plate. Shape changes
could be induced, in one embodiment, as follows:
If all actuators are simultaneously charged (discharged) so that they
expand (contract), the plate will expand (contract) biaxially. According
to this aspect of the invention, there may be a lesser extent of thickness
expansion (contraction), determined primarily by the expansion
anisotropy designed into the multilayer actuator. The net macroscopic
expansion of the plate depends, according to this aspect, and in one
embodiment, on the area or volume fraction of actuators and details of
load transfer. The actuator fraction may be, in one embodiment, 50% or
more, so that an actuator exhibiting 10% volume expansion results in a
5% expansion of the plate.
In one embodiment, the lengthening, shortening, shear, or combination
thereof, of the plate along any direction in the plane of the plate may
be accomplished by actuating the three orientations non-uniformly.
In another embodiment, curvature about any axis or axes may be produced
by actuating the two sides of a plate in a non-uniform manner. For example,
if all actuators on one surface are expanded equally, while those on the
opposing surface either contract equally or are not activated, the plate
will cup in a uniform (macroscopically spherical) curvature. The net
curvature may depend, in another embodiment, on the strain induced at each
surface, the thickness of the plate or combination thereof; for example,
a 2 cm thick plate having +5% expansion at one surface and -5% contraction
at the other may exhibit a radius of curvature of 20 cm.
In another embodiment, twisting, saddle curvatures, or more complex
topologies may be produced by actuating the two sides of a plate
appropriately, which, in another embodiment, may manifest in the depicted
shape changes as shown in FIG. 47.
In another embodiment, the Continuous Fiber Electrochemical Actuator may
be arrayed such that it is applied to the surface of a plate, in one
embodiment, along the 3 orientations herein described, and actuated to
provide multiple morphing capability (FIG. 48C).
In another embodiment, a combination of stacked and fiber actuators may
be used. Higher morphing performance may be achieved, in another
embodiment, by increasing the actuator density within the plate. In
another embodiment, the array may be constructed such that each hexagonal
cell is virtually filled by actuator, for example, as depicted in FIG.
48D. To impart greater thickness expansion or contraction capability
(including varying thickness changes along the plate), the cross-section
of the plate may, in another embodiment, also contain stacked actuators
(for example, as depicted in 48D, panel 2).
It is to be understood that the present invention encompasses any
embodiment, or combinations of embodiments for what is to be considered
an electrochemical actuator of this invention, and the invention includes
any structure, fabric, device, etc. comprising the same, or multiples
thereof. It is to be understood that several actuators may be incorporated
within a single structure, apparatus, device, fabric, that the actuators
may differ, in terms of their type, materials used to construct the
actuator, actuation energy provided, preconditioning, stress
amplification, or strain amplification properties, etc., and are
encompassed by the present invention.
While only a few embodiments of the present invention have been shown and
described, it will be apparent to those persons skilled in the art that
many changes and modifications may be made thereunto without departing
from the spirit and scope of the invention, and numerous applications of
the methods and devices of the invention are apparent, and to be considered
as part of this invention.
The following examples are presented in order to more fully illustrate
the preferred embodiments of the invention. They should, in no way be
construed, however, as limiting the broad scope of the invention.
EXAMPLES
Example 1
Electrochemical Actuator Utilizing LiFePO.sub.4-Based Electrode and
Porous Ceramic Separator
FIG. 1, from Yamada [J. Electrochem. Soc., 148, A224 (2001)] shows the
volume changes that occur in the olivine structure compound
(Fe,Mn)PO.sub.4 as it is lithiated to the end-member composition
Li(Fe,Mn)PO.sub.4. Between the fully lithiated (upper curve) and fully
delithiated (lower curve) limits of composition, a volume change of
7.4-10% (linear strain of 2.4-3.2%) is realizable depending on the Fe/Mn
ratio. FIG. 4 illustrates a design of electrochemical actuator in which
a positive electrode is used with a porous alumina separator of high
stiffness and load bearing ability. The negative electrode comprises Li
metal, which is deposited within the pores of the porous load-bearing
actuator so that it is not load bearing, while still providing a source
and sink for Li ions during the operation of the actuator. An actuator
of this design was constructed using a positive electrode for a
rechargeable lithium battery having a 100 .mu.m thick composite layer
comprising an LiFePO.sub.4-based cathode active powder, polymer binder,
and carbon conductive additive, deposited on an aluminum foil current
collector of about 15 micrometer thickness. The electrode had an area of
about 1 cm.sup.2. A 2 mm thick porous alumina separator was used, sectioned
from a glass-bonded alumina abrasive product (Norton Company, Worcester,
Mass.). On the negative electrode side of this separator, a small amount
of Li metal was mechanically squeezed into the pores of the separator,
and a copper foil negative current collector was applied. The assembly
was infiltrated with a liquid electrolyte used for lithium rechargeable
cells (LP40), sealed in a polymer envelope, and subjected to 1 MPa uniaxial
prestress applied normal to the layers of the actuator. The actuator was
cycled over a voltage range of 2.0-4.0V at a constant 0.2 mA current. The
actuator required 8 charge/discharge cycles for the layers to adjust, and
on the 9.sup.th cycle, the expected expansion upon discharge was seen as
Li+ was intercalated into the LiFePO.sub.4 positive electrode, FIG. 1B,
with 2.3% linear strain being observed, in good agreement with the
expected value.
In another example, a 200 mm thick layer (typical for battery electrodes)
of the electrochemical insertion compound in FIG. 1, when formulated as
a powder-based composite electrode, will have a Young's modulus of Y=50
GPa (reduced from the single crystal value of .about.150 GPa). Under 3.3V
applied voltage this electrode can be fully intercalated to reach a linear
strain of .epsilon..about.1.5%, thereby generating
e.sup.33=3.8.times.10.sup.4 C/m.sup.2. The strain energy density (FIG.
4), taken as 1/2Y.epsilon..sup.2/.rho. where .rho. is the material
density, is estimated at .about.2050 J/kg (5.6.times.10.sup.6 J/m3) for
the active material layer, and .about.1000 J/kg (2.8.times.10.sup.6
J/m.sup.3) for an actuator stack containing one-half by weight or volume
of inactive supporting layers. For a stack volumetric strain energy
density of 2.8.times.10.sup.6 J/m.sup.3, at 1.5% linear strain the
equivalent blocked stress should be .about.375 MPa.
Example 2
Multilayer Stacked Actuator Using LiCoO.sub.2 and Carbon as Active
Materials
In FIG. 1C, actuation is shown in a multilayer stacked actuator in which
the positive electrode is LiCoO2 and the negative electrode is carbon.
These devices are commercially available batteries fabricated according
to the "Bellcore" gel-electrolyte technology in which positive electrode
and negative electrode layers (about 30 layers total) are bonded together
with a bondable separator film, following which the multilayer stack is
packaged in polymer. Typical cells are shown in FIG. 2. The laminates are
oriented normal to the plane of the cell. This battery is elastically soft
due to the materials used; it is a relatively low energy density device
containing a large fraction of soft polymer components to facilitate
manufacturing. The cells were tested in the as-received state with no
preconditioning prior to electromechanical testing. The cells were tested
in an apparatus designed to apply a constant pre-stress between two
parallel-faced rams while the cells were charged and discharged. The
deformation of the cells in the direction of applied stress was measured
with a precision displacement transducer. Under 1 MPa applied pressure,
a reversible 1% linear expansion was measured, as shown in FIG. 1C,
providing for an energy density of 10 kJ/m.sup.3.
FIG. 3 shows results for a cell under various values of pre-stress from
1 MPa to 5 MPa. For this cell the strain is .about.0.7% at 1 MPa, and
decreases as the pre-stress is increased. In the as-received condition,
the cells have a Young's modulus measured in the direction of actuation
(normal to the face of the cells and the planar electrode layers)
of .about.30 MPa. The maximum actuation energy density in this device
is .about.12 kJ/m.sup.3. FIG. 4 shows results from a cell that exhibited
higher energy density. In this instance the applied pre-stress is 3.5 MPa,
and the strain exhibited by the cell is .about.1%, yielding a mechanical
energy density of .about.35 kJ/m.sup.3. This actuation energy density is
approximately one-half that of a typical well-engineered PZT
piezoelectric actuator.
Example 3
Multilayer Stacked Actuators and Preconditioning for Improved
Performance
Multilayer stacked actuators can have several different internal
constructions, as exemplified in the following. FIG. 5 shows several
lithium ion rechargeable cells based on LiCoO.sub.2-carbon chemistry,
each of which has a different internal construction. Each of these designs
was demonstrated to be capable of performing substantial mechanical work,
and furthermore, to have improved performance after preconditioning
treatments described herein.
Several samples of each cell were double-vacuum-bagged in plastic and
placed in an isostatic press, and the pressure raised to 45,000 psi and
held for 5 minutes. After testing, the open circuit voltage of the cells
was measured, and all cells were found to have survived the pressure
treatment without suffering an internal short. The capacity of the
batteries changed only slightly after the isopressing treatment, showing
a reduction in capacity measured between 3.0 and 4.2V at a C/5 or C/2.5
rate of <3% for the 120 mAh and 150 mAh cells, and .about.8% for the 200
mAh cells. A significant volume reduction was seen for each cell. FIG.
6 is a plot of the volume reduction for 10 cells of one type, in which
volume reductions ranging from 3.45% to 10.25% were observed. An excess
volume in the cell may exist, which can be reduced by the pressing
treatment. FIG. 6 also tabulates the macroscopic densities measured by
the Archimedes method of each cell type before and after isopressing. The
average volume reduction ranges from 1.4% to 5.4%. It is also seen that
the density of the actuators is low, from 2.15 to 2.39 g/cm.sup.3, which
may be compared to the density of a PZT piezoelectric actuator of
approximately 7.5 g/cm.sup.3.
These multilayer cells were found to exhibit viscoelastic deformation
under a uniaxial stress applied normal to the largest face of the prismatic
cell, which is normal to the plane of the electrode in the stacked cases.
Both as-received and isopressed cells exhibited viscoelastic relaxation.
FIG. 7 shows the relaxation in applied stress over time when a cell is
subjected to 10 MPa stress in an Instron test machine. The stress is ramped
to 10 MPa at a crosshead speed of 0.002 in/min, and then the crosshead
is stopped so that no further displacement occurs. Over time, the stress
then relaxes substantially. However, with each successive stressing and
relaxation cycle, the amount of stress relaxation decreases, and
eventually the cell is able to sustain nearly the full applied pressure
of 10 MPa. Furthermore, the thickness of the cells increased after the
stress was removed at the end of the test, and increased by 2.5 to 4% over
a period of several hours. These results show that multilayer stacked
actuators of such design using powder composite electrodes, microporous
polymer separators, and polymer packaging exhibit viscoelastic
relaxation properties, but that the dimensions of the cells can be
stabilized by applying stress over an extended time prior to using them
as electrochemical actuators.
Under uniaxial applied stress, these cells were found to be able to
withstand extremely high applied stresses before internal
short-circuiting. Using the Instron apparatus, stress was increased at
a constant crosshead speed while the cell voltage (at a 3.8 Vstate of
charge initially) was continuously monitored. For the 120 mAh, 150 mAh,
and 200 mAh cells respectively, the voltage did not decrease until
pressures of 37 MPa, 57 MPa, and 67 MPa respectively were reached. Thus
electrochemical actuators of these designs may be expected to be tolerant
to high and abusive stress conditions.
The apparent Young's modulus was measured on these cells in the direction
normal to the largest area faces after the isopressing treatments. The
cells showed two characteristic slopes in the stress-strain relationship,
a lower slope between zero and 5 MPa exhibiting a modulus of 50-60 MPa,
and a higher slope above 10 MPa exhibiting a modulus of 220-320 MPa.
Clearly, a more compressible component or components of the cells provide
for the Lower stiffness, which after compression transfers load to higher
modulus constituents. It is also shown that even the lower modulus value
is greater than the modulus of .about.30 MPa measured in as-received cells
prior to preconditioning, thereby demonstrating a benefit of the
preconditioning treatment. These results show that there exist regimes
of lower and higher stiffness for the multilayer stacked actuators, in
which the accessible actuation energy densities may accordingly vary.
The volume expansion of the cells was precisely measured in a fluid
displacement apparatus. FIG. 8 shows the reversible volumetric expansion
of .about.1.5% that was measured on a 150 mAh cell. Other cells showed
similar values of reversible volume expansion. Thus, these measurements
show the capability of electrochemical actuators to perform volume
expansion mechanical work as described in multiple embodiments of the
present invention. These test results also show that for a multilayer
stacked actuator, the expansion is anisotropic, since the volumetric
expansion is less than the linear expansion described below. Anisotropic
expansion is advantageous for certain applications of electrochemical
actuators.
The charge-discharge curves, corresponding strain, and strain energy
density of these multilayer stacked actuators measured after the
preconditioning treatment are shown in FIGS. 9-12. The measurements were
made with an Instron apparatus under conditions where a constant stress
was applied, and the displacement was allowed to vary, with charging and
discharging of the cells at a C/5 rate. In FIG. 9, there was nearly constant
cyclic strain on top of creep strain. The capacity remains constant with
cycling. 1.5%-1.9% strain and an energy density of 75-95 kJ/m.sup.3 was
observed. In general, a cyclic strain paralleling the charge-discharge
cycle is observed, which is superimposed upon a background creep
relaxation as noted earlier. As shown in FIG. 12, at up to about 10 MPa
stress, strains of 1.5% or larger are readily obtained, and energy
densities increase with applied stress up to 10 MPa, reaching peak values
of about 150 kJ/m.sup.3. At higher stresses, such as 15 and 20 MPa,
actuation strain is diminished but so is the capacity of the cell,
indicating that the limiting factor is ion transport rather than the
ability of the active material to be charge/discharged under the
particular applied stress. It is probable that the higher applied stresses
cause the porosity in the separator and/or the particle-based electrodes
to be decreased, thereby lowering the rate capability of the cells. Thus,
the use of higher modulus separators and electrode constructions as
embodied else where in this patent application can allow electrochemical
actuation to higher stresses.
Example 4
High Rate Actuation in Multilayer Stacked Electrochemical Actuators
In order to demonstrate that multilayer stacked actuators can exhibit high
strains and actuation energy densities with rapid rates of actuation and
that substantial actuation performance can be obtained using only partial
charge and discharge of an electrochemical cell, a different actuator was
used. The cells tested were commercially available LiCoO.sub.2-carbon
lithium ion cells (Kokam), having a prismatic form factor with dimensions
of 59.times.33.5.times.5.4 mm.sup.3. The cells have a nominal capacity
quoted by the manufacturer of 740 mAh and are rated for up to 20 C
continuous discharge. They use a microporous polymer separator in an
accordion-folded construction alternating layers of the electrodes, as
shown for the bottom cell in FIG. 5. An aluminum current collector is used
at the positive electrode, and a copper current collector at the negative
electrode. Tests were conducted under a constant 2 MPa uniaxial stress.
These cells exhibit actuation strains of about 2% under a 2 MPa constant
stress. The cells were cycled at 2.96 A (4 C), 3.70 A (5 C), and 4.44 A
(6 C) for five cycles for a specified amount of time (1 min, 2 min, 5 min,
10 min). Between charging and discharging, a 5 minute rest period was used
to allow the voltage to relax. Before charging, a constant voltage
discharge to 3 V was used to ensure a fully discharged cell, however, a
constant voltage hold was not used in the charged state before discharging.
FIGS. 13 and 14 show the cyclic actuation strain obtained versus the cycle
number, at different values of constant current. At higher currents, more
capacity is achieved in the charge/discharge time, and the strain
increases. In all of the plots, testing conducted using lower current
followed by successively higher current. Note that substantial strains
are obtained in very short actuation times, for example at the 4.44 A rate
(6 C) rate, 0.3%, 0.65%, 1.25%, and 1.75% strain are obtained in 1, 2,
5, and 10 minutes respectively. FIG. 15 shows the charging actuation
strain versus capacity. It is noted that the strain increases
monotonically with the capacity to which the cell is charged, such that
a desired strain level can be selected by charging for a selected time.
In all cases, that discharge capacity (and strain) is less than charge
capacity may be due to differences in the total current passed during the
charge and discharge cycles under test conditions, and can be readily
adjusted by changing the charge and discharge profile, as described in
other embodiments. For this cell, the manufacturer's prescribed charge
profile is to use CC-CV at 0.5 C to 4.2 V. However, the fastest charge
to any capacity is obtained by a direct constant voltage charge at 4.2
V, with a limiting current set to the maximum rated 14.8 A.
Example 5
Stacked Actuator from High Density Electrodes
LiCoO.sub.2-based and graphite-based electrodes of conventional design
typical of those used in the lithium ion battery field were used to form
a bi-layer stacked actuator, shown in FIG. 16. This actuator differs from
those in preceding examples which have used commercially available cells
in that the electrode formulation has been selected according to methods
well-known to those skilled in the art to provide a higher packing density
and a higher stiffness. Accordingly, the completed actuator exhibits
higher stiffness and lower viscoelastic relaxation than in the preceding
examples. In addition, the negative electrode uses a platelet graphite
which during processing takes on a preferred crystallographic texture
with the c-axis preferentially aligned in the desired actuation direction.
Consequently, the strains obtained are greater than in the commercially
available cells, and may be greater than expected for the
LiCoO.sub.2-graphite system under the conditions where the graphite is
not preferentially aligned.
The electrodes were prepared by coating a formulation incorporating a
powder of the respective active material, a polymer binder, and a
conductive carbon additive, dispersed in an organic solvent. The
LiCoO.sub.2 coating (510) was applied to one side of an aluminum foil
current collector (570) while the graphite coating (530) was applied to
one side of a copper foil current collector (560). The Al was laminated
on a polymer film. The LiCoO.sub.2 on Al foil had the following properties:
125 um, 55 vol %, .about.1 cm.times..about.1 cm. The graphite on Cu-foil
had the following properties: 85 um, 70.3% vol %, .about.1
cm.times..about.1 cm. After drying and pressing, a cell was assembled as
shown in FIG. 16. A conventional polymer separator (520) was used, and
a conventional organic carbonate electrolyte (LP30) (550) was used. The
active thickness of the electrode was 210 um and the total thickness
was .about.0.6 mm. The measured electrode modulus is .about.100 mPa (14.5
ksi).
FIGS. 17 and 18 show the charge-discharge voltage curves and the
corresponding strain measured in this cell, measured under 1 MPa and 10
MPa pre-stress respectively. Under 1 MPa pre-stress, FIG. 17, a strain
of 3-4.3% was observed, corresponding to an actuation energy density
of .about.45 kJ/m3. Under 10 MPa prestress, FIG. 18, a strain of 2-3% was
observed, corresponding to an actuation energy density of .about.300
kJ/m3. FIG. 19 shows results from another actuator of the same type, tested
under 10 MPa and 17 MPa uniaxial applies stress. In this instance, 2.3%
and 1.8% strain, and 230 kJ/m.sup.3 and 300 kJ/m.sup.3 energy density,
are obtained respectively at 10 and 17 MPa. It is further noted that under
17 MPa, the rate of strain with capacity is the same as at the lower
pressures even though the total strain is less, which indicates that the
full capacity of the cell is not reached for kinetic reasons such as the
compression of porosity in the polymer separator, but that the active
material has not substantially changed its actuation performance. It is
understood that with improvements in design as described in other
embodiments, still higher strains and strain energy densities may be
obtained from actuators using electrodes of this type.
The electrodes of this example were further coated on both sides of their
respective current collector foils and assembled into a multilayer
stacked actuator having a thickness of about 6 mm. These cells were tested
under varying prestress levels, using a so-called CCCV profiles in which
the voltage range was 3.0-4.2V, and a constant C/5 current was applied
until the 4.2 charge voltage or 3.0 discharge voltage was reached, at which
point the voltage was held constant until the current decayed to less than
C/50. A 10 minute rest at constant voltage and zero current was also
conducted between charge and discharge portions. FIGS. 20 to 22 show the
strain obtained under 1, 5 and 10 MPa stress, at corresponding portions
of the charge-discharge curve. Note that at 1 MPa, a high strain of 4.1%
is obtained. At 10 MPa, the strain is still 2.5%, and the corresponding
energy density is 249 kJ/m.sup.3. Here also, the capacity of the cell
decreases with increasing stress, showing that it is charge/discharge
kinetics that are limiting the achieved strain and mechanical energy
density and not the intrinsic capability of the active materials used.
Example 7
Segmented Multi-Element Electrochemical Actuator
Highly oriented pyrolytic graphite (HOPG), which is a near-single-crystal
form of graphite, was used as the actuation material. The direction of
actuation was selected to be normal to the graphene sheets, namely along
the c-axis of graphite, as shown in FIG. 23. Along this direction, the
free strain of graphite is 10.4% and the Young's modulus is 35 GPa. In
order to have high mechanical loading along this direction while
intercalating ions transverse to this direction, the HOPG was
laser-machined into a square array of 25 square posts, each of 0.2
mm.times.0.2 mm dimension at the top, and 0.4 mm height. Lithium was used
as the ion intercalant. A conventional LiCoO.sub.2 composite electrode
on aluminum foil current collector was assembled proximally to the HOPG
posts as shown in FIG. 23. The two electrodes were separated by an
insulating polymer separator film, and packaged in polymer sheet as shown
for the actuator in FIG. 16.
FIG. 24 shows the actuation strain of this actuator under 100 MPa
pre-stress. While only partial lithiation of the graphite was achieved,
the resulting strain was .about.1%, yielding an actuation energy density
of .about.1000 kJ/m3. This is more than 10 times the typical actuation
energy density of a PZT piezoelectric actuator.
In another actuator of this type, an array of small posts was carved from
a piece of HOPG, which was 1 cm square and 1 mm thick, by laser
micromachining. The dimensions of the posts were 0.2 mm square at the top
and 0.7 mm square at the bottom, and the height was 0.4 mm. The surface
of the substrate part and that at the top of the posts were parallel to
the graphite layers. A SEM image of the sample is shown in FIG. 25.
A three layer assembly of copper foil, polypropylene membrane and another
copper foil was attached on the substrate, surrounding the HOPG posts.
The lower copper foil was attached on the surface of the substrate part.
Lithium foil was put on the upper copper foil and used as a counter
electrode. The polypropylene membrane insulated the two copper foils. FIG.
25 schematically shows the cross-section of the sample. The sample was
sealed in a bag of aluminum-laminate film filled with liquid electrolyte.
The electrolyte used was 1.33 M LiPF.sub.6 dissolved in a mixed solvent
of ethylene carbonate, propylene carbonate, dimethyl carbonate, and ethyl
methyl carbonate (4:1:3:2 by volume). The sample was measured in a strain
apparatus in which various preloads could be applied along the normal to
the surface. The sample was cyclically charged and discharged, and the
change in thickness was simultaneously measured by a precision
displacement transducer equipped on the apparatus.
FIG. 26 shows strain and voltage as functions of time during a
charge-discharge cycle by a constant current of 0.4 mA under a mechanical
preload of 100 MPa. The sample was first discharged until voltage became
less than 0.01 V, then it was charged until voltage became more than 2
V. The curves clearly show that the strain was induced by the charge and
discharge. The linear strain is 1.2% during the discharge, and this
corresponds to a mechanical energy density of 1,200 kJ/m.sup.3.
In another sample of this type, a layer of HOPG was bonded to an alumina
plate. A piece of HOPG, which was 5 mm square and 0.4 mm thick, was first
bonded to an alumina substrate, which was 12 mm square and 0.6 mm thick,
with 25 .mu.m thick copper foil at 650.degree. C. for 1 hour in vacuum
under a stress of 50 MPa. The HOPG piece was bonded so that the graphite
layers were parallel to the surface of the substrate. An array of small
posts was carved from the HOPG part by laser micromachining. The
dimensions of the posts were 0.2 mm square at the top and 0.35 mm square
at the bottom, and the height was 0.4 mm.
A triple layer of copper foil, polypropylene membrane and another copper
foil was attached on the substrate, surrounding the HOPG posts. The lower
copper foil was attached to the copper layer that was used to bond the
HOPG part. Lithium foil was put on the upper copper foil and used as a
counter electrode. The polypropylene membrane insulated the two copper
foils. The sample was sealed in a bag of aluminum-laminate film filled
with liquid electrolyte. The electrolyte used was 1.33 M LiPF.sub.6
dissolved in a mixed solvent of ethylene carbonate, propylene carbonate,
dimethyl carbonate, and ethyl methyl carbonate (4:1:3:2 by volume). The
sample was measured in a strain apparatus in which various preloads could
be applied along the normal to the surface. The sample was cyclically
charged and discharged, and the change in thickness was simultaneously
measured by a precision displacement transducer equipped on the apparatus.
FIG. 26B shows strain and voltage as functions of time during a
charge-discharge cycle under a preload of 30 MPa. The sample was discharge
at a current of 0.05 mA until voltage became 0.01 V, followed by additional
discharge at a voltage of 0.01 V until the current decayed to less than
0.005 mA. Then, it was charged at a current of 0.05 mA until the voltage
became more than 1 V, followed by additional charge at 1 V until the current
decayed to less than 0.005 mA. The linear strain is 4.3% during and
mechanical energy density is 1,290 kJ/m.sup.3.
It is understood that with engineering improvements well-understood to
those skilled in the art of electrochemical materials and devices, greater
intercalation and greater corresponding strain is achievable. For example,
the width of the posts may be narrowed in order to increase the extent
of lithiation under a given current rate. At complete lithiation
giving .about.10% linear expansion, the actuation energy density under
100 MPa pre-stress is 10,000 kJ/m.sup.3.
It is also understood that many segmentation patterns may be applied to
this basic actuator design to improve load-bearing and intercalation. FIG.
27 shows one alternative design in which the posts are more widely spaced
so as to distribute the load over a larger macroscopic area, in which
instance the lithiation source may be placed between the load-bearing
posts.
Example 8
Large Stroke Electrochemical Lever Actuator
Large stroke electrochemical lever actuators may be prepared, and
represent additional embodiments of the invention. A lever and fulcrum
mechanism are used to amplify the induced strain of multilayer
electrochemical actuators, hereafter referred to as the "active elements"
to distinguish from the actuator, which comprises these as well as a
mechanical assembly and optionally other sensors and controls for
controlling the performance of the actuator. This actuator benefits from
a simple amplification mechanism, easy method of applying prestress at
the actuator output, and an ideal and compact form factor for placing the
actuator in small spaces, exemplified by, but not limited to, such
applications as actuating a rotor blade spar for trailing edge or rotor
blade twisting actuation, deploying flaps in aircraft, watercraft, and
land vehicles, deforming a mirror in an adaptive optical device, deploying
solar panels in a satellite, latching or unlatching a door or lid, or
opening and closing a valve.
Measurements of displacement under preload, actuation force, and device
stiffness have been conducted on the ELA. The results show that actuators
based on this approach are capable of performing significant mechanical
work. The mechanical performance of the electrochemical lever actuator
(ELA) was characterized using different kinds of active elements. The
results show that electrochemical actuators based on solid state active
compounds should be attractive for applications where high strain, high
energy density and high actuation authority are desirable.
The design of the ELA is shown schematically in FIG. 28a, and with
dimensional details in FIGS. 29a and 29b. While an actuator of similar
design in which piezoceramics are used as the active materials is
available commercially for micropositioning applications (Physik
Instrumente, there are, in some embodiments, functional advantages in
using electrochemical actuation elements in an actuator of this type,
including but not limited to the ability to generate much larger stroke.
Referring to FIG. 28a, the amplification ratio, given by the ratio of the
displacement at the actuator output relative to the displacement of the
active elements (here a stack of individual elements), is given by b/(a/2).
The actuator of the example was designed to have an amplification ratio
of six.
A stiffness analysis illustrates advantages of the present actuator
compared to comparable piezo-powered devices. As shown by E. F. Prechtl
and S. R. Hall (Design of a high efficiency, large stroke
electromechanical actuator, MIT, Cambridge, Mass. 1998), to obtain the
highest coupling efficiency the stiffness of the expansive element, in
this case the active elements, should be much lower than the stiffness
of the coupler, in this case the elastic flexure. This is readily
accomplished in the present case since, as shown in preceding examples,
electrochemical actuators can be fabricated with stiffness much lower
than that of many structural metals, ceramics, and composites. In addition,
in order to reduce performance losses due to bending in the lever arm,
the bending moment in the flexure should be low compared to the bending
moment in the lever arm. These considerations led to the design shown in
FIG. 27.
Although the flexure can in principle be fabricated from numerous
materials, in this example the frame was constructed of stainless steel
with a Young's modulus of E=170 GPa. This frame, having outer dimensions
130 mm.times.32 mm.times.50 mm, transmits the load from the actuation
elements to the actuator output. A cavity of dimensions of 80 mm.times.20
mm.times.40 mm was machined in the frame to accommodate the actuation
elements. The flexure having the dimensions in FIG. 27 was then realized
by making a series of precision wire-EDM (Electric Discharge Machining)
cuts (Model: ROBOFIL240CC from Charmilles Technologies SA).
End caps were made of the same stainless steel as the support frame. They
have a spherical surface with a radius of 20 mm and a thickness of 15 mm
for one end cap and 10 mm for the other. The radius of the end caps can
also be increased to reduce Hertzian losses at the contacts. Shims were
also made of stainless steel in thicknesses from 0.1 mm to 0.8 mm and were
used to fulfil the preload methodology of the ELA.
A preload is applied easily at the actuator output, see FIG. 27. A
compressive preload is necessary to eliminate mechanical backlash, and
to maximize the actuator force and stroke output. When the electrochemical
active elements exhibit creep strain under load, shims can be used between
the end caps and the actuator element stack to ensure that the creep strain
is taken up under compressive preload.
A multitude of tests were conducted to characterize the performance of
the ELA, using actuator elements of prismatic form factor similar to those
discussed in preceding examples. Displacement tests were carried out with
different compressive preloads. The preload was applied with an Instron
apparatus (Model 5550 and Bluehill control software) at a load rate of
460 N/h for most tests. After a desired peak preload value was reached,
a rest period was used to allow for creep deformation of the active
elements. The active elements were connected in parallel and
simultaneously charged and discharged for multiple cycles at various
rates, using the CCCV protocol. The amplified displacement at the actuator
output was measured by the Instron crosshead, using a test rod with a
spherical surface of 5 mm diameter made of tungsten was used to transmit
the induced displacement and load from the actuator output to the strain
gage and the load cell of the Instron crosshead.
For example, the output strain measured under a load of 270N results in
a stress of 4 MPa on the active elements. The output average displacement
during charging is 3.42 mm, and for discharging is 3.72 mm, approximately
an order of magnitude greater than can be expected from a lever actuator
using piezoceramic elements. With these values and the amplification
factor we calculate a battery stack strain of approx. 1.5%, which is
consistent with the strains shown in preceding examples for these active
elements under a few MPa stress. This implies a much higher stiffness for
the frame than for the active elements, as is desired, and a high
mechanical efficiency for the device.
Example 9
Electrochemical Woven Actuator
An Electrochemical Woven Actuator (EWA) was designed, as part of this
invention, whose properties allow for very large stroke and high force
actuation. While the embodiment described herein, for this actuator was
developed for operation in a helicopter rotor blade, it is also suitable
for other engineering applications requiring large stroke actuation.
One of the main challenges in developing a novel actuator with the
intercalation compounds was that the induced strain of the compounds has
an actuation direction not identical to the direction required for many
engineering applications. Considering this limitation, the development
of actuation mechanisms that transform the principal strain direction of
the active element (i.e., a multilayer electrochemical actuator) into the
appropriate direction required for the application was sought. One
desirable aspect of the actuator sought was to enclose the active elements
with a layer of woven fibers, and to generate the strain and force of the
actuator in the horizontal direction by extending the active element
vertically. FIG. 30 shows the schematic view of the actuator, where three
active elements (1) are enclosed by two alternating fibers (2). On the
top and bottom surfaces of each active element, a cap with a constant
curvature (3) is attached to provide a uniform normal stress. Clearly,
a vertical extension of the active element reduces horizontal
displacement of the actuator, and therefore, a contraction force is
generated in the horizontal direction.
We constructed a first prototype EWA by using stainless steel wires as
the weaving material, and tested its performance to validate its concept.
The active elements comprised three commercial batteries, each one of them
with its caps machined from aluminum and attached with epoxy glue. The
geometry of the EWA was chosen to maximize the energy efficiency of the
device, while the resulting thickness of the EWA is acceptable. In order
to test the performance of the EWA, it was subjected to a constant load
while the batteries were charged, as shown in FIG. 31(a). The actuator
strain was measured and compared with the strain in one of the batteries.
The measurements showed a smaller strain than expected, due to some creep
which was produced in large part by the commercial lithium ion cells used
as active elements. If, however, the creep is removed from the data, a
strain very close to the predicted value is obtained. FIG. 31(b) shows
the graph obtained from the test, with the creep portion removed.
FIG. 31 provided predicted values, and in FIG. 32 the expected stiffness
and strain bounds were plotted against the ratio of the actuator length
L and the battery length w, which demonstrated good correspondence.
Example 10
Actuated Beams
It was also of interest to construct an actuated beam, as shown in FIG.
33. One face of the beam was mechanically constrained by two layers of
a fiberglass weave. 27 actuators were arrayed as shown in FIG. 33, and
epoxy resin was poured as the matrix for the beam. The 27 actuators were
electrically joined in parallel, and a power source was used to charge
and discharge them within the voltage limits specified by the manufacturer
(ATL Corporation). The beam was tested by clamping one end and using a
laser beam as a "light lever" to measure the deflection of the other end.
Upon charging and discharging, the tip of the beam deformed by 1 mm. This
corresponds to a surface strain of 400 microstrain. Thus it is
demonstrated that the electrochemical actuators of the invention can be
used to provide mechanical actuation in a beam structure.
Example 11
Electrochemically Based Fluidics Actuator
While electrochemical pumping of a gas with a solid electrolyte has been
used in prior art to perform actuation, a high stress is not possible,
due to the compressibility of the gas. Since liquids have much less
compressibility than gases their utilization produces greater actuation
authority.
In this concept an electrolytic membrane, which pumps an ion from one side
of a device to another, generating a liquid rather than a gas in the process,
is used. By pumping a liquid, much higher actuation forces can be produced
since liquids have much lower compressibility. Actuators of this kind can
be used in fluidic and micro fluidic devices, micro hydraulic devices,
nastic structures compressing cellular micro-fluidic or micro hydraulic
devices, and others.
A proton-conducting membrane may be utilized to transport hydrogen ions
to produce water, resulting in a net volume expansion (FIG. 34). Upon
charging, for each mole of H+ transported across the membrane, producing
one mole of water, from one half mole of OH, there is a net volume change:
.times..times..times..times..times..times..times..times..times..times
..times..times..times..times..times..times..times..times..times..times..t
imes.
##EQU00001## .times..times..times..times..times..times..times..times.
.times..times..times..times..times..times..times..times..times..times..times..times..t
imes.- .times..times..times..times..times..times. ##EQU00001.2##
Thus the volume expansion is:
.times..times..times..times..times..times. ##EQU00002##
5 7,909,893 Electrode for a lithium battery, method for production of
such an electrode and lithium battery comprising said electrode
United States Patent
Le Cras ,
7,909,893
et al.
March 22, 2011
Abstract
The invention relates to a lithium battery, comprising at least one
lithium intercalation compound, made up of crystallites and obtained by
a production method, comprising at least the following steps: formation
of a homogeneous mixture of at least one precursor for the lithium
intercalation compound with a given adjunct, chemically stable with
relation to crystallites and designed to limit the growth of crystallites
or crystallite precursors during the formation thereof, thermal treatment
of the homogeneous mixture for the synthesis of the lithium intercalation
compound in the form of crystallites and to give a composite material
comprising at least two phases formed respectively by the lithium
intercalation compound and the adjunct and forming of the composite
material to give said electrode. The invention further relates to an
electrode obtained by said method and lithium battery comprising such an
electrode.
Inventors:
Le Cras; Frederic (Notre Dame de l'Osier, FR),
Martinet; Sebastien (Grenoble, FR), Bourbon; Carole
(Saint-Michel de Saint-Geoirs, FR), Launois; Sebastien
(Grenoble, FR)
Assignee:
Commissariat a l'Energie Atomique (Paris, FR)
Appl. No.:
11/631,168
Filed:
July 21, 2005
PCT Filed:
July 21, 2005
PCT No.:
PCT/FR2005/001889
371(c)(1),(2),(4)
December 29, 2006
Date:
PCT Pub. No.:
WO2006/018514
PCT Pub. Date:
February 23, 2006
Foreign Application Priority Data
Jul 26, 2004 [FR]
04 08246
Current U.S. Class:
Current International
Class:
Field of Search:
29/623.1 ; 429/231.95; 502/101
4/58
H01M 4/82 (20060101); H01M
(20100101); H01M 4/88 (20060101)
29/623.1,623.3-623.5
429/208-209,218.1-227,229,231,231.2-231.95
502/101
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Other References
Wang, Zhaoxiang et al. "Structural and electrochemical
characterizations of surface-modified LiCoO2 cathode materials
for Li-ion batteries," Solid State Ionics, vol. 148, 335-342 pp
(2002). cited by other .
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Primary Examiner: Yuan; Dah-Wei D
Assistant Examiner: (Rademaker) Roe; Claire L
Attorney, Agent or Firm: Oliff & Berridge, PLC
Claims
The invention claimed is:
1. A method for production of an electrode for a lithium battery including
a composite material, the composite material comprising a first phase
formed by a lithium intercalation compound made up of crystallites and
a second phase constituted by a selected specific additional compound,
the method comprising at least the following steps: forming the composite
material, wherein forming the composite material comprises: forming a
homogeneous mixture of at least one precursor of the lithium intercalation
compound with the selected specific additional compound; and synthesizing
the lithium intercalation compound by heat treatment of the homogeneous
mixture, wherein the selected specific additional compound is different
from the precursor and is chemically stable with respect to crystallites
and to said precursor under the synthesis conditions of the lithium
intercalation compound, to limit the growth of the crystallites, and
wherein the selected specific additional compound is selected from the
group consisting of oxides, nitrides, carbides, borides and silicides of
at least one chemical element selected from manganese, calcium, yttrium,
lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum, tungsten, aluminum, cerium, iron, boron and silicon;
and shaping of the composite material so as to obtain said electrode.
2. The method according to claim 1, wherein the specific additional
compound is selected from the group consisting of Y.sub.2O.sub.3,
Al.sub.2O.sub.3, TiO.sub.2, ZrO.sub.2, CeO.sub.2, HfO.sub.2,
Cr.sub.2O.sub.3, La.sub.2O.sub.3, Fe.sub.2O.sub.3, FeAl.sub.2O.sub.4,
CaO, MgO, MgAl.sub.2O.sub.4, MgCr.sub.2O.sub.4 and Y.sub.2TiO.sub.5, TiC,
B.sub.4C, SiC, ZrC, WC, NbC and TaC, TiN, BN, Si.sub.3N.sub.4 and AlN,
TiB.sub.2 and VB.sub.2 and MoSi.sub.2.
3. The method according to claim 1, wherein the shaping step comprises
at least application of the composite material on a metallic support.
4. The method according to claim 1, wherein at least one further compound
selected from the group consisting of carbon and metals is added to the
composite material between the thermal treatment step and the shaping step.
5. The method according to claim 1, wherein the composite material has
a weight ratio between the proportion of the additional compound and the
proportion of the lithium intercalation compound is lower than or equal
to 0.2.
6. The method according to claim 1, wherein the crystallites have a size
less than or equal to 2 .mu.m in the composite material.
7. The method according to claim 6, wherein the size of the crystallites
in the composite material is less than or equal to 200 nm.
8. The method according to claim 1, wherein the additional compound is
in form of a film having a thickness less than or equal to 200 nm, the
crystallites being dispersed in said film.
9. The method according to claim 8, wherein the thickness of the film is
less than or equal to 20 nm.
10. The method according to claim 1, wherein the additional compound is
in the form of particles having a diameter less than or equal to 200 nm
and separating the crystallites.
11. The method according to claim 10, wherein the diameter of the particles
of the additional compound is less than or equal to 20 nm.
Description
BACKGROUND OF THE INVENTION
The invention relates to a method for production of an electrode for a
lithium battery comprising at least a lithium intercalation compound made
up of crystallites.
The invention also relates to an electrode obtained by one such method
and to a lithium battery comprising one such electrode.
STATE OF THE ART
Lithium batteries are tending to replace nickel-cadmium (Ni--Cd) or
nickel-metal hydride (Ni-MH) storage batteries as autonomous energy
source in portable equipment. The performances and more particularly the
specific and volume energy densities of lithium batteries and of
lithium-ion batteries are in fact higher than those of Ni--Cd and Ni-MH
batteries.
The positive electrode of lithium batteries generally comprises an active
compound called ion intercalation compound, such as TiS.sub.2, NbSe.sub.3,
V.sub.2O.sub.5, LiCoO.sub.2, LiNiO.sub.2, LiMn.sub.2O.sub.4 and
LiV.sub.3O.sub.8.
In lithium-ion batteries, the intercalation compound LiCoO.sub.2
presents very good electrochemical properties. However, the limited
quantity and the price of cobalt are an obstacle to such lithium-ion
batteries in applications requiring high storage capacities becoming
generalized.
Moreover, replacing the cobalt by nickel or manganese is not satisfactory.
LiNiO.sub.2 is in fact chemically unstable in the de-intercalated state,
i.e. in the charged state for the battery. LiNiO.sub.2 can then form active
oxygen by disproportionation and the active oxygen formed is liable to
react with the organic solvents of the electrolyte causing the battery
to explode.
The LiMn.sub.2O.sub.4 compound, stable at room temperature, is liable to
be attacked by small quantities of HF contained in the electrolyte, above
a temperature of about 55.degree. C. This attack then causes dissolution
of the manganese and a rapid and irreversible drop in the battery capacity.
For example, in the article "Low temperature synthesis characterization
and evaluation of LiMn.sub.2O.sub.4 for lithium ion battery (Canadian
metallurgical quarterly, vol 43, pages 89 to 93), S. Sengupta and al.
obtain a manganese and lithium oxide by means of a low-temperature method,
which oxide presents a higher discharge behaviour than that of a material
available on the market. S. Sengupta and al. attribute this improved
efficiency to the sub-micron size of the crystallite of the synthesized
powder.
It has been proposed to replace lithium and transition metal oxides by
materials having a isotype structure of olivine, more particularly of
LiMPO.sub.4 type, where M is a metal such as iron. For example, the
reversible insertion and de-insertion reaction of lithium in LiFePO.sub.4
is as follows: LiFe.sup.IIPO.sub.4Fe.sup.IIIPO.sub.4+Li.sup.+e.sup.Thus, when this reaction takes place, the iron goes reversibly from a +II
oxidation state to a +III oxidation state, a cation Li.sup.+ and an
electron then being released. However the insertion and de-insertion
potential of the LiFePO.sub.4 compound, i.e. the electrochemical
potential of the FePO.sub.4/LiFePO.sub.4 couple, is 3.43V with respect
to the electrochemical potential of the Li.sup.+/Li couple. Furthermore,
the specific capacity of LiFePO.sub.4 is 170 mAh/g. These two values
enable a theoretical specific energy density of 580 Wh/Kg to be obtained,
whereas the practical specific energy density of LiCoO.sub.2 is about 530
Wh/kg.
It is however difficult to implement a practical specific energy close
to the theoretical value of LiFePO.sub.4. Indeed, LiFePO.sub.4 not having
a mixed valency and the nature of the path which the electron has to take
in the olivine structure give to the LiFePO.sub.4 compound an electronic
insulator nature. Substitutions have been attempted to generate a mixed
valency iron compound but they did not provide any real progress from an
electrochemical point of view.
To remedy this drawback and to obtain a positive electrode that is
sufficiently electron-conducting, it is common practice to add carbon to
the LiFePO.sub.4 compound in proportions varying between 10% and 15% in
weight. Thus, in the article "Conductivity improvements to spray-produced
LiFePO.sub.4 by addition of a carbon source (Materials letters 58 (2004)
pages 1788 to 1791), S. L. Bewlay and al. propose to achieve a composite
material of LiFePO.sub.4/C type for a positive electrode of a lithium-ion
battery by pyrolitic spraying, adding sucrose designed to form the carbon
to the LiFePO.sub.4 precursors. But as carbon is a reducer, it can lead
to formation of the phosphide compound, at the surface of the LiFePO.sub.4
grains, which is liable to destroy a part of the intercalation material.
Furthermore, as the density of the composite material obtained is not
sufficient, the active volume does not enable such a composite material
to be used in any type of application.
OBJECT OF THE INVENTION
It is one object of the invention to provide a method for production of
an electrode for a lithium battery that is easy to implement and enables
a good electronic conductivity and a high efficiency of the lithium
insertion and de-insertion reaction to be obtained.
According to the invention, this object is achieved by the appended claims.
More particularly, this object is achieved by the fact that the method
comprises at least the following steps: formation of a homogeneous mixture
of at least one precursor of the lithium intercalation compound with a
specific additional compound that is chemically stable with respect to
crystallites and designed to limit the growth of crystallites during
formation thereof, thermal treatment of the homogeneous mixture so as to
synthesize the lithium intercalation compound in the form of crystallites
and to obtain a composite material comprising at least two phases
respectively formed by the lithium intercalation compound and by the
additional compound, and shaping of the composite material so as to obtain
said electrode.
It is a further object of the invention to provide an electrode for a
lithium battery obtained by such a method for production and remedying
the shortcomings of the prior art. More particularly, the object of the
invention is to provide an electrode having an improved lithium insertion
and de-insertion reaction efficiency.
According to the invention, this object is achieved by the fact that the
electrode comprises at least one composite material comprising at least
two phases respectively formed by a lithium intercalation compound made
up of crystallites and by an additional compound that is chemically stable
with respect to the crystallites and designed to limit the growth of
crystallites during formation thereof.
It is a further object of the invention to provide a lithium battery
comprising one such electrode and presenting a high efficiency.
According to the invention, this object is achieved by the fact that the
lithium battery comprises at least a first electrode according to the
invention, an electrolyte and a second electrode, the second electrode
comprising at least one material chosen from metallic lithium, a lithium
alloy, a nanometric mixture of a lithium alloy and of a lithium oxide,
a material of spinel structure comprising lithium and titanium, a lithium
and transition metal nitride, carbon and a lithium intercalation compound.
BRIEF DESCRIPTION OF THE DRAWING
Other advantages and features will become more clearly apparent from the
following description of particular embodiments of the invention given
as non-restrictive examples only.
A voltage/specific energy capacity curve of a particular embodiment of
a lithium battery according to the invention is represented in the
accompanying FIG. 1.
DESCRIPTION OF PARTICULAR EMBODIMENTS
A lithium battery comprises at least first and second electrodes,
respectively positive and negative, and an electrolyte. In the lithium
secondary battery, the positive electrode comprises at least a active
compound generally called lithium insertion compound or lithium
intercalation compound. The intercalation compound is formed by
crystallites also called crystallized solid particles.
The lithium intercalation compound can for example comprise an oxide
chosen from titanium, vanadium, chromium, manganese, iron, cobalt, nickel,
molybdenum and niobium oxides and combinations thereof. Such an oxide can
also be substituted or combined with lithium oxide, sulphides or selenides
of one or more elements chosen from iron, molybdenum, niobium and titanium.
It can also be combined with mixed phosphates, silicates or borates of
lithium and of an element chosen from titanium, vanadium, chromium,
manganese, iron, cobalt, nickel, molybdenum and niobium or with metals
or aluminium-based, silicon-based, germanium-based and/or tin-based
alloys.
Such an active compound presents the property of successively inserting
and de-inserting Li.sup.+ cations, when the lithium battery is operating,
during the charging and discharging operations.
According to the invention, the lithium intercalation compound is
associated in the electrode with a specific additional compound designed
to improve the kinetics of the lithium intercalation and de-intercalation
reaction, while limiting the growth of crystallites constituting the
lithium intercalation compound during formation thereof. What is meant
by limiting the growth of crystallites during formation thereof is that
the growth of crystallites, and if applicable that of lithium
intercalation compound precursors, are limited during synthesis of the
lithium intercalation compound or during a subsequent re-crystallization
should this be the case.
Adding an additional compound in the electrode, which compound limits the
growth of crystallites and is chemically stable with respect to
crystallites and preferably refractory, in fact enables the mean distance
of the path covered by the electrons in the lithium intercalation compound
to be shortened. It enables the efficiency of the lithium insertion and
de-insertion reaction to be increased, in particular for reaction
kinetics compatible with operating regimes comprised between 0.5 and 2
C. The weight ratio between the proportion of additional compound and the
proportion of lithium intercalation compound is preferably lower than or
equal to 0.2.
More particularly, improvement of the efficiency of the lithium insertion
and de-insertion reaction is obtained by formation of a stable composite
material comprising two distinct phases. A first phase is in fact formed
by crystallites and is designed to react according to the lithium
insertion and de-insertion reaction. The second phase consists of the
additional compound having the function of limiting the growth of the
crystallites during formation thereof. The second phase is also
chemically stable with respect to crystallites, i.e. it does not react
chemically with the crystallites in the conditions of synthesis of the
latter, of recrystallization or subsequently. The composite material thus
formed can also be associated with a further compound chosen from carbon
and metals which, due to their intrinsic electronic conductivity, improve
the electronic conductivity of the composite material.
The presence of a specific additional compound in the electrode thus
enables crystallites of small sizes to be obtained thereby reducing the
diffusion length of the electrons in the electrode. The additional
compound in fact forms a physical shield against diffusion, in solid phase,
of the crystallites constituting the intercalation compound, and this
shield limits crystalline growth. Moreover, even the crystallites located
at the heart of the electrode, due to their small size, can react in
accordance with the reversible lithium insertion and de-insertion
reaction.
The additional compound is preferably chosen from the group comprising
oxides, nitrides, carbides, borides and silicides of at least one chemical
element chosen from manganese, calcium, yttrium, lanthanum, titanium,
zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum,
tungsten, aluminium, cerium, iron, boron and silicon. More particularly,
it is chosen from the group comprising Y.sub.2O.sub.3, Al.sub.2O.sub.3,
TiO.sub.2, ZrO.sub.2, CeO.sub.2, HfO.sub.2, Cr.sub.2O.sub.3,
La.sub.2O.sub.3, Fe.sub.2O.sub.3, FeAl.sub.2O.sub.4, CaO, MgO,
MgAl.sub.2O.sub.4, MgCr.sub.2O.sub.4 and Y.sub.2TiO.sub.5, TiC,
B.sub.4C, SiC, ZrC, WC, NbC and TaC, TiN, BN, Si.sub.3N.sub.4 and AlN,
TiB.sub.2 and VB.sub.2 and MoSi.sub.2. Such compounds are particularly
suitable to be additional compounds designed to reduce the size of the
crystallites. In addition, they are chemically stable and
electrochemically stable when the lithium secondary battery is in
operation. Moreover, for equal growth limiting and chemical and
electrochemical stability performances, the choice of the additional
compound is preferably determined by the highest electronic conduction
capacity.
Moreover, the additional compound is preferably chosen such as to limit
the size of the crystallites to a value less than or equal to 2 .mu.m and
more particularly less than or equal to 200 nm. This limiting of the size
of the crystallites is obtained by limiting the growth of the crystallites,
in particular during synthesis of the lithium intercalation compound or
during recrystallization thereof after mechanical damage.
The additional compound can be in the form of a film having a thickness
less than or equal to 200 nm, and preferably less than or equal to 20 nm.
The composite material is then in the form of crystallites of the lithium
intercalation compound dispersed in a film formed by the additional
compound. As this film has to let the Li.sup.+ ions pass, it is therefore
either discontinuous or continuous but porous to Li.sup.+ ions.
The additional compound can also be in the form of solid particles having
a diameter less than or equal to 200 nm and preferably less than or equal
to 20 nm, and the crystallites are arranged between said particles. In
this case, the composite material preferably comprises support elements
designed to maintain the cohesion between the different particles. Such
a support element can be formed by an organic binder or by any other means.
An electrode for a lithium battery is preferably produced by homogeneously
mixing at least one precursor of the lithium intercalation compound with
the additional compound. Then thermal treatment of the homogeneous
mixture is performed so as to synthesize the lithium intercalation
compound in the form of crystallites and to obtain a composite material
comprising at least two phases respectively formed by the lithium
intercalation compound and by the additional compound. Then the material
composite is shaped as an electrode by any type of known means. It can
for example be applied on a metal support.
For example, 0.1 mole of dihydrate ferric (II) oxalate (FeC.sub.2O.sub.4,
2H.sub.2O) and 0.1 mole of monobasic lithium phosphate (LiH.sub.2PO.sub.4)
with 0.00245 mole of yttrium oxide (Y.sub.2O.sub.3) are inserted in a
planetary mill in an argon atmosphere. FeC.sub.2O.sub.4 and
LiH.sub.2PO.sub.4 are in powder form and form the precursors of the
lithium intercalation compound LiFePO.sub.4 whereas Y.sub.2O.sub.3, in
the form of particles having a diameter of 23 nm, forms the additional
compound limiting the formation of LiFePO.sub.4 crystallites. The powders
are then mixed homogeneously for 48 hours in the planetary mill. The
mixture collected then undergoes thermal treatment for one hour at
600.degree. C. in an argon atmosphere so as to synthesize the lithium
intercalation compound LiFePO.sub.4. A composite material in powder form
is then obtained and qualitative and quantitative analysis by X-ray
diffraction shows the presence of the LiFePO.sub.4 phase in the composite
material and indicates that it comprises 96.5% weight of LiFePO.sub.4,
3.5% weight of Y.sub.2O.sub.3 and traces of carbonaceous residues.
85.5% weight of the composite material are then mixed with 6.0% weight
of polyvinylidene fluoride, 5.67% weight of graphite, and 2.83% weight
of acetylene black. This mixture is then stirred with anhydrous
n-methylpyrrolidine so as to obtain a homogeneous fluid ink. The ink is
then applied to an aluminium foil strip by means of a micrometric doctor
blade, and the strip and ink assembly is then dried at 120.degree. C. to
form an electrode of a lithium battery.
Such an electrode is then inserted in a lithium secondary battery of button
cell type comprising a negative electrode made of metallic lithium and
a microporous separator made of polypropylene imbibed with an electrolyte
comprising a mixture of ethylene carbonate (EC) and dimethyl carbonate
(DMC), LiPF.sub.6. As illustrated in FIG. 1, the voltage/specific
capacity curve of the lithium battery thus formed shows that the
theoretical capacity achieved, at a charging/discharging rate of C/2, is
compatible with the operating conditions necessary for portable
applications for which the charging operation is performed in a maximum
of one or two hours whereas the discharging operation has to be slow,
taking place in about 10 hours.
The invention is not limited to the embodiments described above. Thus it
also relates to a lithium battery comprising a first electrode according
to the invention, a second electrode and an electrolyte. The second
electrode can be formed by any type of material known to be used in lithium
batteries. It can for example be constituted by a material forming a
Li.sup.+ cation source for the positive electrode. The lithium source
constituting the negative electrode is for example chosen from metallic
lithium, a lithium alloy, a nanometric mixture of a lithium alloy and a
lithium oxide, a lithium and transition metal nitride.
In the case where the negative electrode is not formed by a lithium source
for the positive electrode, it is formed by a lithium intercalation or
insertion material such as carbon in graphite form or a material of spinel
structure containing lithium and titanium. In this case, the lithium is
never present in metallic form in the lithium battery, the Li.sup.+
cations then going backwards and forwards between the two lithium
insertion materials of the negative and positive electrodes, on each
charging and discharging of the battery.
In this case, the negative electrode can also comprise an additional
compound designed to limit the size of the crystallites constituting the
lithium insertion material, and possibly also carbon and an organic binder.
Furthermore, the electrolyte of the lithium battery can be formed by any
type of known material. It can for example be formed by a salt comprising
at least the Li.sup.+ cation. The salt is for example chosen from
LiClO.sub.4, LiAsF.sub.6, LiPF.sub.4, LiR.sub.FSO.sub.3,
LiCH.sub.3SO.sub.3, LiN(R.sub.FSO.sub.2).sub.2,
LiN(R.sub.FSO.sub.2).sub.3, R.sub.F being chosen from a fluorine atom and
a perfluoroalkyl group comprising between 1 and 8 carbon atom. The salt
is preferably dissolved in an aprotic polar solvent and can be supported
by a separating element arranged between the first and second electrodes,
the separating element then being imbibed with electrolyte. The salt can
also be mixed with a molten salt such as imidazolium salts and derivatives
thereof, pyridinium salts and derivatives thereof and quaternary ammonium
salts.
It has already been proposed to add an additional compound to the lithium
intercalation compound of an electrode, without the added additional
compound however enabling the size of the crystallites forming the
intercalation compound to be limited, when formation thereof takes place.
For example, the Patent Application EP-A-1403944 describes a positive
electrode made of "boronized" graphitic material and the method for
producing same. The "borated" graphitic material is a compound of a solid
solution in which the carbon atoms are partially substituted by boron
atoms or by a boron compound such as boron carbide, cobalt boride or
hafnium boride. However, unlike the invention, the boron atom or the boron
compound in the Patent Application EP-A-1403944 is not chemically stable
with respect to the graphitic material constituting the lithium
intercalation compound and it is not designed to limit the growth of
crystallites during formation thereof. Consequently, the "boronized"
graphitic material does not form a stable composite material with two
distinct phases. Adding boron or a boron compound, in the Patent
Application EP-A-1403944, is on the contrary designed to stabilize the
crystalline structure of the graphitic material by introducing partial
defects, so as to modify the crystallographic structure of the graphitic
material.
6 7,883,644 Stoichiometric lithium cobalt oxide and method for
preparation of the same
Abstract
A LiCoO.sub.2-containing powder. and a method for preparing a
LiCoO.sub.2-containing powder, includes LiCoO.sub.2 having a
stoichiometric composition via heat treatment of a lithium cobalt oxide
and a lithium buffer material to make an equilibrium of a lithium chemical
potential therebetween; the lithium buffer material which acts as a Li
acceptor or a Li donor to remove or supplement a Li-excess or a
Li-deficiency, the lithium buffer material coexisting with the
stoichiometric lithium metal oxide. Also an electrode includes the
LiCoO.sub.2-containing powder as an active material, and a rechargeable
battery includes the electrode.
7 7,867,657 Electrolyte for non-aqueous cell and non-aqueous
secondary cell
Abstract
In a rechargeable non-aqueous electrolyte secondary battery using
positive electrodes, negative electrodes and a non-aqueous electrolytic
solution, additives to the electrolytic solution are used in combination,
preferably in combination of at least two compounds selected from
o-terphenyl, triphenylene, cyclohexylbenzene and biphenyl, and thus
there are provided batteries excellent in safety and storage
characteristics.
8 7,867,471 Process for preparing advanced ceramic powders using
onium dicarboxylates
Abstract
A process of producing a ceramic powder including providing a plurality
of precursor materials in solution, wherein each of the plurality of
precursor materials in solution further comprises at least one
constituent ionic species of a ceramic powder, combining the plurality
of precursor materials in solution with an onium dicarboxylate
precipitant solution to cause co-precipitation of the ceramic powder
precursor in a combined solution; and separating the ceramic powder
precursor from the combined solution. The process may further include
calcining the ceramic powder precursor.
9 7,864,507 Capacitors with low equivalent series resistance
Abstract
An electric double layer capacitor (EDLC) in a coin or button cell
configuration having low equivalent series resistance (ESR). The
capacitor comprises mesh or other porous metal that is attached via
conducting adhesive to one or both the current collectors. The mesh is
embedded into the surface of the adjacent electrode, thereby reducing the
interfacial resistance between the electrode and the current collector,
thus reducing the ESR of the capacitor.
10 7,862,927 Thin film battery and manufacturing method
Abstract
In a method of fabricating a battery, a substrate is annealed to reduce
surface contaminants or even water of crystallization from the substrate.
A series of battery component films are deposited on a substrate,
including an adhesion film, electrode films, and an electrolyte film. An
adhesion film is deposited on the substrate and regions of the adhesion
film are exposed to oxygen. An overlying stack of cathode films is
deposited in successive deposition and annealing steps.
11 7,862,627 Thin film battery substrate cutting and fabrication process
Abstract
A method of fabricating a battery comprises selecting a battery substrate
having cleavage planes, and cutting the battery substrate with pulsed
laser bursts from a pulsed laser beam to control or limit fracture along
the cleavage planes. The pulsed laser beam was also found to work well
on thin substrates which are sized less than 100 microns. Before or after
the cutting step, a plurality of battery component films can be deposited
on the battery substrate. The battery component films include at least
a pair of electrodes about an electrolyte which cooperate to form a
battery.
12 7,851,078 Secondary battery with a shock absorbing portion
Abstract
A secondary battery includes an electrode assembly, a can receiving the
electrode assembly, and a cap assembly coupled to the open upper part of
the can. In addition, a vent including an opening, which is thinner than
the can is formed on a wide side of the can, and a shock absorbing portion,
which is thinner than the can and thicker than the opening, is formed near
the vent. Accordingly, the vent can be protected from damage from external
shocks, which are absorbed by the shock absorbing portion.
13 7,846,579 Thin film battery with protective packaging
Abstract
A battery comprises a substrate comprising an electrolyte between a pair
of conductors, at least one conductor having a non-contact surface. A cap
is spaced apart from the non-contact surface of the conductor by a gap
having a gap distance d.sub.g of from about 1 .mu.m to about 120 .mu.m.
The gap allows the conductor to expand into the gap. The gap is further
bounded by side faces about a surrounding perimeter that may be sealed
with a seal. In one version, the ratio of the surface area of the
non-contact surfaces on the conductor to the total surface area of the
side faces is greater than about 10:1. A pliable dielectric can also be
provided in the gap.
14 7,791,317 Battery pack and method of calculating deterioration level
thereof
Abstract
A battery pack is disclosed. The battery pack includes at least one battery,
a switch section, a measurement section, and a deterioration level
calculation section. The switch section turns on and off charging to the
battery. The measurement section measures an open circuit voltage of the
battery. The deterioration level calculation section calculates the
deterioration level of the battery based on the open circuit voltage
measured by the measurement section after the switch section has
repeatedly turned on and off the charging 10 times or more.
15 7,776,776 Method for preparing catalyst platinum supported on
lithium cobalt oxide
Abstract
The present invention relates to a method for preparing catalyst platinum
supported on lithium cobalt oxide for sodium borohydride hydrolysis. The
catalyst with crystalline platinum is produced by mixing dihydrogen
hexachloroplatinumate and black lithium-cobalt-oxide powder with the
impregnation method, and then by a two-step sintering. Platinum is the
major catalytic activity site, and lithium cobalt oxide is the support
thereof. The manufacturing process of the present invention is simple,
and can be applied to catalytic reactions or electrocatalytic reactions
in fuel cells. Thereby, the present method is very practical to industry.
16 7,776,478 Thin-film batteries with polymer and LiPON electrolyte
layers and method
Abstract
A method and apparatus for making thin-film batteries having composite
multi-layered electrolytes with soft electrolyte between hard
electrolyte covering the negative and/or positive electrode, and the
resulting batteries. In some embodiments, foil-core cathode sheets each
having a cathode material (e.g., LiCoO.sub.2) covered by a hard
electrolyte on both sides, and foil-core anode sheets having an anode
material (e.g., lithium metal) covered by a hard electrolyte on both sides,
are laminated using a soft (e.g., polymer gel) electrolyte sandwiched
between alternating cathode and anode sheets. A hard glass-like
electrolyte layer obtains a smooth hard positive-electrode lithium-metal
layer upon charging, but when very thin, have randomly spaced
pinholes/defects. When the hard layers are formed on both the positive
and negative electrodes, one electrode's dendrite-short-causing defects
on are not aligned with the other electrode's defects. The soft
electrolyte layer both conducts ions across the gap between hard
electrolyte layers and fills pinholes.
17 7,776,476 Battery
Abstract
A battery capable of improving cycle characteristics is provided. A
spirally wound electrode body in which a cathode and an anode are wound
with a separator in between is included. An electrolytic solution in which
an electrolyte salt is dissolved in a solvent is impregnated in the
separator. The electrolytic solution contains a cyclic ester carbonate
derivative having halogen atom such as 4-fluoro-1,3-dioxolan-2-one and
a light metal salt such as difluoro[oxolate-O,O']lithium borate,
tetrafluoro[oxolate-O,O']lithium phosphate, and difluoro
bis[oxolate-O,O']lithium phosphate.
18 7,745,054 Non-aqueous electrolyte and lithium secondary battery
comprising same
Abstract
An electrolyte for a lithium secondary battery includes lithium salts,
a non-aqueous organic solvent, and additive compounds, which initiates
decomposition at 4V to 5V and show a constant current maintenance plateau
region of more than or equal to 0.5V at measurement of LSV (linear sweep
voltammetry). The additive compounds added to the electrolyte of the
present invention decompose earlier than the organic solvent to form a
conductive polymer layer on the surface of a positive electrode by
increased electrochemical energy and heat at overcharge. The conductive
polymer layer prevents decomposition of the organic solvent. Accordingly,
the electrolyte inhibits gas generation caused by decomposition of the
organic solvent during high temperature storage, and also improves safety
of the battery during overcharge.
19 7,732,096 Lithium metal oxide electrodes for lithium batteries
Abstract
An uncycled preconditioned electrode for a non-aqueous lithium
electrochemical cell including a lithium metal oxide having the formula
xLi.sub.2-yH.sub.yO.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 in which
0<x<1, 0<y<1 and 0<z<1, M is anon-lithium metal ion with an average
trivalent oxidation state selected from two or more of the first row
transition metals or lighter metal elements in the periodic table, and
M' is one or more ions with an average tetravalent oxidation state selected
from the first and second row transition metal elements and Sn. The
xLi.sub.2-yH.sub.y.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 material
is prepared by preconditioning a precursor lithium metal oxide (i.e.,
xLi.sub.2M'O.sub.3.(1-x)LiMO.sub.2) with a proton-containing medium
with a pH<7.0 containing an inorganic acid. Methods of preparing the
electrodes are disclosed, as are electrochemical cells and batteries
containing the electrodes.
20 7,731,765 Air battery and manufacturing method
Abstract
A battery (10) is disclosed having a lithium foil anode (11) embedded
within a liquid electrolyte (12) which is positioned between two similarly
constructed battery cathode halves (13) and (14). Each cathode half has
a first glass barrier (16) coupled to a first porous metal substrate (17),
a second glass barrier (18) coupled to a second porous metal substrate
(19), a third glass barrier (20) coupled to a third porous metal substrate
(21), and a lithium air cathode (22). A peripheral layer of edge sealant
(25) surrounds the peripheral edge of the electrolyte and bonds the two
halves together. The battery also includes an anode terminal (27) coupled
to the anode and a cathode terminal (28) coupled to the cathode.
21 7,721,936 Interlock and surgical instrument including same
22 7,721,931 Prevention of cartridge reuse in a surgical instrument
23 7,713,660 Method for manufacturing manganese oxide nanotube or
nanorod by anodic aluminum oxide template
24 7,709,151 Non-aqueous electrolyte secondary battery, positive
electrode active material and method of manufacturing the same
25 7,695,649 Lithium transition metal oxide with gradient of metal
composition
26 7,692,411 System for energy harvesting and/or generation, storage,
and delivery
27 7,682,735 Pouch type lithium secondary battery and method of
fabricating the same
28 7,678,503 Surface and bulk modified high capacity layered oxide
cathodes with low irreversible capacity loss
29 7,678,498 Nonaqueous electrolyte secondary battery
30 7,662,515 Nonaqueous electrolyte battery, battery pack and vehicle
31 7,648,794 Lithium secondary battery and a cap assembly therefor
32 7,579,117 Electrochemical cell energy device based on novel
electrolyte
33 7,566,479 Method for the synthesis of surface-modified materials
34 7,563,540 Cathode active material and lithium secondary battery
using the same
35 7,547,493 Lithium cobalt oxide, method for manufacturing the same,
and nonaqueous electrolyte secondary battery
36 7,547,492 Lithium cobalt oxide, method for manufacturing the same,
and nonaqueous electrolyte secondary battery
37 7,541,715 Electrochemical methods, devices, and structures
38 7,540,886 Method of manufacturing lithium battery
39 7,524,393 Gel electrolyte battery
40 7,510,582 Method of fabricating thin film battery with annealed
substrate
41 7,507,501 Positive active material composition for rechargeable
lithium batteries
42 7,459,236 Battery
43 7,410,730 Thin film battery and electrolyte therefor
44 7,393,476 Positive electrode active material for lithium secondary
cell and lithium secondary cell
45 7,381,395
Non-aqueous electrolyte secondary battery and method of
manufacturing the same
46 7,364,793 Powdered lithium transition metal oxide having doped
interface layer and outer layer and method for preparation of the same
47 7,338,734 Conductive lithium storage electrode
48 7,314,682 Lithium metal oxide electrodes for lithium batteries
49 7,295,878 Implantable devices using rechargeable zero-volt
technology lithium-ion batteries
50 7,267,907 Negative electrode for rechargeable lithium battery and
rechargeable lithium battery comprising same
51 7,258,821 Nickel-rich quaternary metal oxide materials as cathodes
for lithium-ion and lithium-ion polymer batteries
52 7,253,494 Battery mounted integrated circuit device having
diffusion layers that prevent cations serving to charge and discharge
battery from diffusing into the integrated circuit region
53 7,248,929 Implantable devices using rechargeable zero-volt
technology lithium-ion batteries
54 7,241,533 Electrode for rechargeable lithium battery and
rechargeable lithium battery
55 7,238,450 High voltage laminar cathode materials for lithium
rechargeable batteries, and process for making the same
56 7,211,237 Solid state synthesis of lithium ion battery cathode
material
57 7,204,862
Packaged thin film batteries and methods of packaging
thin film batteries
58 7,186,479 Thin film battery and method of manufacture
59 7,184,836 Implantable devices using rechargeable zero-volt
technology lithium-ion batteries
60 7,177,691 Implantable pulse generators using rechargeable zero-volt
technology lithium-ion batteries
61 7,166,387 Thin battery with an electrode having a higher strength
base portion than a tip portion
62 7,160,415 Gel electrolyte battery
63 7,150,940 Lithium ion secondary battery
64 7,105,203 Intermittent coating apparatus and intermittent coating
method
65 7,056,622 Nonaqueous electrolyte secondary battery
66 7,041,336 Intermittent coating apparatus and intermittent coating
method
67 7,033,705 Polymer electrolyte, rechargeable lithium battery and
method of preparing rechargeable lithium battery
68 6,982,132 Rechargeable thin film battery and method for making the
same
69 6,962,613 Low-temperature fabrication of thin-film energy-storage
devices
70 6,932,922 Lithium cobalt oxides and methods of making same
71 6,902,745 Method of manufacturing nano-sized lithium-cobalt
oxides by flame spraying pyrolysis
72 6,886,240 Apparatus for producing thin-film electrolyte
73 6,882,130 Battery-driven electronic device and mobile
communication apparatus
74 6,878,490 Positive electrode active materials for secondary batteries
and methods of preparing same
75 6,869,724 Non-aqueous electrolyte secondary battery and positive
electrode for the same
76 6,866,965 Polymeric electrolyte and lithium battery employing the
same
77 6,852,139 System and method of producing thin-film electrolyte
78 6,841,303 High ionic conductivity gel polymer electrolyte for
rechargeable polymer batteries
79 6,835,493
Thin film battery
80 6,821,679 Fabrication method of LiCoO2 nano powder by surface
modification of precursor
81 6,819,084 Method of fabricating rechargeable lithium battery and
rechargeable lithium battery fabricated by same
82 6,818,356 Thin film battery and electrolyte therefor
83 6,806,685 Accumulator power supply unit
84 6,805,991 Nonaqueous electrolyte solution secondary battery
85 6,758,404 Media cipher smart card
86 6,755,873 Gel electrolyte battery
87 6,737,196 Method of making a lithium polymer battery and battery
made by the method
88 6,733,927 Non-aqueous electrolyte secondary battery and method
for manufacturing the same
89 6,713,987 Rechargeable battery having permeable anode current
collector
90 6,682,849 Ion battery using high aspect ratio electrodes
91 6,667,132 Non-aqueous electrolyte secondary batteries
92 6,653,019 Non-aqueous electrolyte secondary cell
93 6,652,605 Process for preparation of a lithiated or overlithiated
transition metal oxide, active positive electrode materials containing this
oxide, and a battery
94 6,623,886 Nickel-rich quaternary metal oxide materials as cathodes
for lithium-ion and lithium-ion polymer batteries
95 6,613,479 Positive electrode material and battery for nonaqueous
electrolyte secondary battery
96 6,613,478 Positive electrode material and cell for nonaqueous
electrolyte secondary battery
97 6,596,439 Lithium ion battery capable of being discharged to zero
volts
98 6,582,481 Method of producing lithium base cathodes
99 6,562,518 Fabrication of highly textured lithium cobalt oxide films
by rapid thermal annealing
100 6,562,218 Method for forming a thin film
101 6,555,270 Fabrication of highly textured lithium cobalt oxide films
by rapid thermal annealing
102 6,553,263 Implantable pulse generators using rechargeable
zero-volt technology lithium-ion batteries
103 6,528,204 Lithium secondary battery comprising individual cells
with one another, as well as watches, computers and communication
equipment provided with a battery
104 6,527,955 Heat-activatable microporous membrane and its uses in
batteries
105 6,511,516 Method and apparatus for producing lithium based
cathodes
106 6,503,432 Process for forming multilayer articles by melt extrusion
107 6,461,762 Rechargeable battery structure having a stacked structure
of sequentially folded cells
108 6,428,933 Lithium ion batteries with improved resistance to
sustained self-heating
109 6,423,453 Solid electrolyte battery
110 6,423,106 Method of producing a thin film battery anode
111 6,402,796 Method of producing a thin film battery
112 6,399,246 Latex binder for non-aqueous battery electrodes
113 6,398,824 Method for manufacturing a thin-film lithium battery by
direct deposition of battery components on opposite sides of a current
collector
114 6,395,426 Non-aqueous electrolyte cell having a positive electrode
with Ti-attached LiCoO2
115 6,387,563 Method of producing a thin film battery having a
protective packaging
116 6,350,543 Manganese-rich quaternary metal oxide materials as
cathodes for lithium-ion and lithium-ion polymer batteries
117 6,348,282 Non-Aqueous electrolyte secondary batteries
118 6,344,366 Fabrication of highly textured lithium cobalt oxide films
by rapid thermal annealing
119 6,291,097 Grid placement in lithium ion bi-cell counter electrodes
120 6,287,722 Continuous melt process for fabricating ionically
conductive articles
121 6,280,883 Bis (perfluoralkanesulfonyl)imide surfactant salts in
electrochemical systems
122 6,280,873 Wound battery and method for making it
123 6,242,129 Thin lithium film battery
124 6,114,062 Electrode for lithium secondary battery and method for
manufacturing electrode for lithium secondary battery
125 6,103,213 Process for producing lithium-cobalt oxide
126 6,094,292 Electrochromic window with high reflectivity
modulation
127 6,090,505 Negative electrode materials for non-aqueous electrolyte
secondary batteries and said batteries employing the same materials
128 6,063,519 Grid placement in lithium ion bi-cell counter electrodes
129 5,914,094 Process for preparing cathode active material by a
sol-gel method
130 5,849,433 Polymer blend electrolyte system and electrochemical
cell using same
131 5,837,015 Method of making a multilayered gel electrolyte bonded
rechargeable electrochemical cell
132 5,834,135 Multilayered gel electrolyte bonded rechargeable
electrochemical cell
133 5,716,421 Multilayered gel electrolyte bonded rechargeable
electrochemical cell and method of making same
134 5,709,968 Non-aqueous electrolyte secondary battery
135 5,688,293 Method of making a gel electrolyte bonded rechargeable
electrochemical cell
136 5,681,357 Gel electrolyte bonded rechargeable electrochemical cell
and method of making same
137 5,639,573 Polymer gel electrolyte
138 5,591,544 Current collector device
139 5,588,971 Current collector device and method of manufacturing
same
140 5,578,396 Current collector device
141 5,573,554 Current collector device and method of manufacturing
same
142 5,567,548 Lithium ion battery with lithium vanadium pentoxide
positive electrode
143 5,508,122 Battery with a spiral electrode unit
144 5,396,177 Battery with electrochemical tester
145 5,339,024 Battery with electrochemical tester
146 5,308,720 Non-aqueous battery having a lithium-nickel-oxygen
cathode
147 5,015,547 Lithium secondary cell
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