New Materials Discovery
(LiFePO4)
(LiFeBO3)
Degradation Study via 7Li MAS NMR
100C_60h
upon degradation
Northeastern Center for Chemical
Energy Storage (NECCES)
Thrust 2: Conversion Chemistry
Thrust 1: Intercalation Chemistry
Study of Electrochemical Processes
Understanding Distribution of Phases
Li in a Fe (III)-rich
environment
100C_36h
100C_12h
Li containing
diamagnetic phase
Pristine
Li in LiFeBO3
2000 1000 0 -1000 -2000
Relative Frequency (ppm)
Lead Institution
Stony Brook University
Partner Institutions
MIT
Rutgers University
SUNY at Binghamton
UC San Diego
University of Michigan
Argonne National Laboratory
Brookhaven National Laboratory
Lawrence Berkeley National Laboratory
Research PI’s
C. P. Grey (Director; Stony Brook University)
M. S. Whittingham (Thrust 1 leader, Binghamton
University)
G. Amatucci (Assoc. Director, Thrust 2 leader,
Rutgers University)
R. Kostecki (Thrust 3 leader, Lawrence Berkeley
National Laboratory)
G. Ceder (Thrust 4 leader, MIT)
R. Bartynski (Rutgers University)
P. Chupas (Argonne National Laboratory)
F. Cosandey (Rutgers University)
S. Garofalini (Rutgers University)
J. Graetz (Brookhaven National Laboratory)
P. Khalifah (Stony Brook University)
Y. S. Meng (UC San Diego)
K. Thornton (University of Michigan)
A. Van Der Ven (University of Michigan)
X.-Q. Yang (Brookhaven National Laboratory)
Director
Theory
C.P. Grey
and Modeling Stony Brook U.
G. Ceder, MIT
Diagnostics
R. Kostecki,
LBNL
Discovering the the ultimate limits to intercalation
reactions for chemical energy storage via studying
model systems using innovative synthesis,
modeling and diagnostic tools.
Thrust 2 – Conversion Materials Development
for Battery Application
Understanding chemical and compositional
perturbations induced by atomic substitutions and
local environment and the elucidation of the
physical and electrochemical mechanisms which
enable conversion systems to work.
Conversion Chemistry
G. Amatucci
Rutgers U.
Pristine
Improving battery performance will be
driven by:
• New materials
• Understanding how the systems
function and why they fail
- new characterization (diagnostics)
methods will play a key role
- theory development to predicting battery
function is critical for materials
improvement and discovery
Discharge
Charge
Thrust 3– Novel Diagnostic Tools to
Investigate Battery Function
Thrust 4 – Theory Development to
Predict Battery Function
Developing in situ methods and multi-functional
probes that push the limits of spatial and temporal
resolution.
Developing models to understand and predict the
kinetics of solid state reactions taking place in
rechargeable Li batteries.
We have focused on new
materials discovery based on the
success story of LiFePO4:
• fast rate performance:
-Li moving along one dimension
• good capacity retention:
-Structure stabilized by strong
covalence of oxoanions: PO43-
LiFeBO3 is a good candidate for
electrodes with fast rate and good
capacity retention. One of the main
issue on LiFeBO3 is an unknown
degradation process which is being
realized by XRD and NMR. We
have discovered methods to
improve the performance.
Thrust 3: Diagnostics
separator
&
electrolyte
V
It is critical to understand how
phases are distributed in a
electrode in order to know how to
maintain electron percolation and
ion conductivity. We have shown
that the distribution of phases can
be realized by state-of-the-art highresolution electron microscopies
(HRTEM and EELS mapping).
Thrust 4: Theory and Modeling
Li metal
Developing in situ Studies
The electrode lithiation and
delithiation involve electrochemical
processes via multi-phase or solidsolution pathway which can be
differentiated
by
the
implementation of synchrotron Xray absorption and scattering
spectroscopies (XANES, EXAFS,
and PDF).
MRI of Electrodes
Modeling Delithiation of LiFePO4
Understanding Hysteresis
calculated
experimental
15 mm
Director
Clare P. Grey
Intercalation Chemistry
M.S. Whittingham,
Binghamton U.
Thrust 1 – Intercalation Materials
Development for Battery Application
Capacity (mAh/g)
0.3 mm
Mission:
Provide major fundamental breakthroughs to address future electrical energy storage technology
requirements and enable a paradigm shift in energy generation and use
Goal:
Identify the key fundamental mechanisms by which electrode materials for rechargeable batteries operate,
and the factors that control the rate and the reversibility of these processes
We
have
designed
and
fabricated a new in situ spectroelectrochemical cell suited for
operando
Synchrotron
X-ray
absorption/scattering (PDF, SAXS,
XAS and XRD) analysis of electrode
materials, compatible with battery
stack used in the conventional 2032
coin cell test setup.
Magnetic Resonance Image
(MRI) provides non-invasive method
to monitor the dendrite formation in
Li and Li ion batteries. MRI of
metals was obtained for the first
time with evidence of dendrite
formation.
necces.chem.sunysb.edu
We have developed a novel
theoretical model for delithiation of
LiFePO4 explaining why it can be
such a high rate material despite its
first order phase transformation – a
very small overpotential leads to a
solid-solution transformation path.
We have also successfully explained
the particle size dependence of the
lithium diffusion constant in LiFePO4.
Large hysteresis is one of the
drawback in conversion materials.
We found from modeling that the
large difference of mobilities of Li
and Cu lead to the voltage
hysteresis found for CuTi2S4. On
discharge lithium is intercalated and
copper de-intercalated/extruded, but
on recharge the copper diffusion is
so slow that Ti2S4 is formed.