Stabilized Lithium Metal Powder (SLMP™) – Material and
Application Technologies for High Energy Li-ion Batteries
Marina Yakovleva, K.B. Fitch, Yangxing Li and Yuan Gao
www.fmclithium.com
Contact info: marina.yakovleva@fmc.com
26th International Battery Seminar & Exhibit,
March 16th-19th, 2009
Market Needs
• New electrode materials are required to increase
energy density of Li-ion batteries
• Li-ion technology has expanded into large format
batteries
• Automotive use demands lower cost and
improved safety
– Need more choices for active and inactive materials!
– Need to break the current limitation that all lithium
has to come from the cathode of the Li-ion cell.
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26th IBS&E, March 16-19th, 2009
Lectro® Max 100 Series, Stabilized Lithium Metal Powder
• Normal lithium powder
– Can only be handled in an argon filled glove box
– Not commercially available as powder
• Stabilized Lithium Metal Powder
(SLMP™)
SEM Image of SLMP
– Safe to handle in a dry room
– Can be transported by air or sea
– Metallic Li content is at least 98%
• FMC has been producing lithium
powder for its own use at the level of
thousands of tons/year for over 30
years
Optical Microscope Image of
SLMP sprayed on the electrode
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26th IBS&E, March 16-19th, 2009
It is a Li-ion System
• The anode host material is lithiated with SLMP to produce a
true Li-ion anode when electrolyte is added at cell activation.
• SLMP provides an independent source of Lithium and it
combines the benefits of the two past systems, which enables
many possibilities for energy and performance enhancements
– Li metal cell : non-lithium providing cathode
– Li-ion cell: host anode material that intercalates lithium
There is NO metallic Li left after cell is activated
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26th IBS&E, March 16-19th, 2009
Benefits of SLMPTM
Opening up choices for active materials
– Anode choice no longer limited to graphite.
•
Allows the use of new materials with both large reversible and irreversible
capacities, such as Si composites and Sn intermetallics.
– Cathode choice no longer limited to lithium providing materials.
•
Much wider selections of non lithium providing materials offering more
possibilities: more overcharge tolerant, lower cost, and larger capacities.
– Use of SLMP™ in battery material synthesis
•
Si and Sn Composite anode materials
Bottom line: increase in energy density, improvements in safety and
calendar life, cost reductions
Using Lithium from SLMP will cost less than using Lithium from LiCoO2 cathode and
you can pocket other advantages too
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26th IBS&E, March 16-19th, 2009
A Cathode Example, MnO2
A Li-ion cell: EMD/Graphite+SLMP ™
Specific Capacity, (discharge mAh/g)
300
200
100
Constant Current 0.1mA, Charge 4.3V, Disharge 1.5V
0
0
5
10
15
20
Cycle Number
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26th IBS&E, March 16-19th, 2009
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30
THE STATE UNIVERSITY OF NEW JERSEY
RUTGERS
A Cathode Example, BiF3
A Li-ion cell: BiF3 Nanocomposite/Graphite+SLMP ™
4
BiF
3.5
3
Cell Voltage
3
2.5
2
"Li
1.5
BiF "
3
vs.Li-1st dis
vs.Li2nd dis
vs.Li 3rd dis
vs.LiMCMB-1st dis
vs.LiMCMB 2nd dis
vs.LiMCMB 3rd dis
BiF Nanocomposite
3
LiPF EC:DMC
6
1
2.45
o
24 C 15 mA/g
0.5
0
2
4
6
8
10
12
Discharge Time (h)
(Data courtesy of Rutgers University)
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26th IBS&E, March 16-19th, 2009
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An Anode Example
First Cycle Efficiency Improvement in Commercial SiO Using SLMP
2.5
2.5
Voltage (V)
Irreversible Capacity
~487 mAh/g
1.5
1.0
Voltage (V)
2.0
2.0
1.5
1.0
0.5
0.5
0.0
0.0
0
200 400 600 800 1000 1200 1400 1600
Irreversible Capacity
~155 mAh/g
0
200
600
800 1000 1200 1400 1600
Capacity (mAh/g)
Capacity (mAh/g)
Baseline Half cell: silicon composite
material
from Shin Etsu Corporation
™
(85%), PI binder (15%), GBL as a
solvent
400
SLMP-treated silicon composite
material from Shin Etsu Corporation
(85%), PI binder (15%), GBL as a
solvent
Test Conditions: constant current charge/discharge, 0.0V to 1.5V
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26th IBS&E, March 16-19th, 2009
Calendar Life Improvements
Cycling Performance of the 5Ah
cells (a) baseline cell (red line),
(b) electrode treated with SLMP
(blue line) with the loading of
1.2% of the MCMB weight, C/2
rate, 3-4.2V range.
Important for long calendar life: SLMP serves as a
“getter” of moisture and acidic species
(Data courtesy of SKC PowerTech Corporation)
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26th IBS&E, March 16-19th, 2009
SLMP™ Introduction into the Cell
Two general methods to apply SLMP™
• Surface application
– Coat an SLMP™ suspension on the surface of pre-fabricated
anode sheet – no need to change the existing anode
fabrication process
• Slurry application
– Include SLMP™ in the slurry mix when the anode sheet is
being cast – no additional step but the slurry solvent needs
to be compatible with lithium.
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26th IBS&E, March 16-19th, 2009
CLEAR
Center for Lithium Energy Advanced Research
• Equipped for demonstration of safe handling of the SLMP Technology
• Equipped for demonstrations of multiple SLMP Application Methods using customer’s
electrodes
• Equipped for making laminated full lithium-ion cells
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26th IBS&E, March 16-19th, 2009
Surface Application
Multiple methodologies have been
evaluated:
•
•
•
•
•
•
A
B
Spraying
Dip Coating
Doctor blade Coating
Dry/Wet Sieving
Printing
painting
Keeping SLMP uniformly distributed
in the suspension is the key
A: SLMP in non-polar solvent without additives, fast separation
B: Additives keep SLMP suspended for extended time periods
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26th IBS&E, March 16-19th, 2009
Spray Application Study-Demonstration (Anode)
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26th IBS&E, March 16-19th, 2009
An Anode Example
A Li-ion cell: LiCoO2/Graphite+SLMP ™
4.5
4.0
Voltage (V)
3.5
3.0
Baseline First Cycle Discharge
Graphite/LiCoO2 Cell
2.5
First Cycle Discharge
SLMP+Graphite/LiCoO2 Cell
2.0
Improvement
1.5
1.0
0.0%
20.0%
40.0%
60.0%
80.0%
100.0%
Capacity
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First Cycle Efficiency Improvement in LiCoO2/Graphite System Using SLMP
(Data courtesy of MaxPower Corporation)
26th IBS&E, March 16-19th, 2009
Spray Application Study-Demonstration (Separator)
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26th IBS&E, March 16-19th, 2009
Optical Microscope Images of the Separator Film
SLMP-treated Electrode
SLMP-treated and pressed Electrode
Open Circuit Voltage (V vs. Li)
Carl Zeiss Axio Imager D1 digital imaging microscope, 100x magnification.
Open circuit voltage for half-cells
Li/graphite/glass paper/Celgard 3501
separator/graphite:
a) Baseline cell (Vo=3.2V)
b) SLMP-treated separator
(Vo=0.14V)
3.0
2.0
Li/MCMB Cell
1.0
Baseline cell
SLMP-treated separator
0.0
0
20
40
60
80
Time (hour)
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26th IBS&E, March 16-19th, 2009
Industrially Scalable Process
•
Set-up designed for the Dcell production with SLMPTM
Technology incorporated
•
under US Army contract
W15P7T-06-C-P242.
Unwind/Rewind
Speed Control
Large Area for spray application
Exhaust Chamber fitted to rewind
portion of machine
B. Meyer and F. Cassel, M. Yakovleva and Y. Gao, and G. Au , 43rd Power Sources
Conference, Philadelphia, Pennsylvania, July 7 – 10, 2008
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26th IBS&E, March 16-19th, 2009
SLMPTM Surface Application
(spray method)
As sprayed
After pressing
26th IBS&E, March 16-19th, 2009
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SLMPTM Surface Application
(spraying method)
Prior to electrolyte addition
Right after electrolyte addition, time=0
time=2 min
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26th IBS&E, March 16-19th, 2009
Time =30 min
SLMP Diffusion into Carbonaceous Anode
26th IBS&E, March 16-19th, 2009
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Thin Li-foil Diffusion into C-Anode
Rolled Li thin foil (<30 micron): macro view
Thin Li foil as applied onto the surface of prefabricated anode
After 7 days of storage at 25oC
After 9 days of
storage at 25oC
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26th IBS&E, March 16-19th, 2009
Thin Li-foil Diffusion into C-Anode
Prior to electrolyte addition
after electrolyte addition, time=1hr
time=1 day
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time=7 days
26th IBS&E, March 16-19th, 2009
New Capabilities: Full Pouch Cells
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26th IBS&E, March 16-19th, 2009
First Cycle Loss
• SLMP Effect on Loss
• Effect of Processing
– Efficiency
– Apparent versus
actual
concentration
10
5
First Cycle Loss (%)
– Performs as if
intercalated from Li
metal
– Optimum
concentration
Baseline
Surfactant
0
0
1
2
3
Surfactant and Carbon
Linear (Baseline)
-5
Linear (Surfactant)
Linear (Surfactant and
Carbon)
-10
-15
Lithium Concentration (%)
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26th IBS&E, March 16-19th, 2009
Summary
• More material choices are needed to meet the increasing demands for
more energy, lower cost and better safety for Li-ion batteries.
• SLMP™ provides an independent source of lithium for Li-ion batteries,
which opens up the choices of both anode and cathode materials to meet
such demands.
• SLMP™ can be introduced into the cell through industrially scalable
methods.
• Lithium from SLMP will be at a lower cost than Lithium from LiCoO2
cathode.
• SLMP™ could be customized to meet specific customer requirements
• Progress in SLMP™ Application Technologies demonstrated
We are welcoming the Battery Community to visit CLEAR and apply SLMP
onto your current and advanced electrode materials and get trained in safe
Lithium handling
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26th IBS&E, March 16-19th, 2009
SLMP Sampling
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26th IBS&E, March 16-19th, 2009
Acknowledgement
Co-workers:
– Scott Petit, Prakash Palepu, Yoshimasa Nomiyama, George Sandor
Rutgers, The State University of New Jersey, ESRG:
– Glenn Amatucci, Irene Plitz, Adam Skrzypczak, Fadwa Badway
MaxPower:
– Frank Cassel, David Chua, Benjamin Meyer
US Army CERDEC:
– George Au
SKC PowerTech
-
Dr. Zhiwei Zhang, Dr. Zhiqiang Xu
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26th IBS&E, March 16-19th, 2009