Director

Clare P. Grey

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)

Northeastern Center for Chemical Energy Storage (NECCES)

necces.chem.sunysb.edu

Theory

and Modeling

G. Ceder, MIT

Diagnostics

R. Kostecki,

LBNL

Intercalation Chemistry

M.S. Whittingham,

Binghamton U.

Conversion Chemistry

G. Amatucci

Rutgers U.

Director

C.P. Grey

Stony Brook U.

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

Discovering the the ultimate limits to intercalation

reactions for chemical energy storage via studying

model systems using innovative synthesis,

modeling and diagnostic tools.

Thrust 1 – Intercalation 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.

Pristine Discharge Charge

Thrust 2 – Conversion Materials Development

for Battery Application

Developing models to understand and predict the

kinetics of solid state reactions taking place in

rechargeable Li batteries.

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.

V

Thrust 3– Novel Diagnostic Tools to

Investigate Battery Function

• 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

New Materials Discovery

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 4: Theory and Modeling

(LiFeBO3) (LiFePO4)

Degradation Study via 7Li MAS NMR

• fast rate performance:

-Li moving along one dimension

•good capacity retention:

-Structure stabilized by strong

covalence of oxoanions: PO43-

We have focused on new

materials discovery based on the

success story of LiFePO4:

2000 1000 0 -1000 -2000 Relative Frequency (ppm)

Pristine

100C_12h

100C_36h

100C_60h

Thrust 3: Diagnostics

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.

Capacity (mAh/g)

The electrode lithiation and

delithiation involve electrochemical

processes via multi-phase or solid-

solution pathway which can be

differentiated by the

implementation of synchrotron X-

ray absorption and scattering

spectroscopies (XANES, EXAFS,

and PDF).

We have designed and

fabricated a new in situ spectro-

electrochemical 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.

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 high-

resolution electron microscopies

(HRTEM and EELS mapping).

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.

Thrust 2: Conversion Chemistry Thrust 1: Intercalation Chemistry

Li metal

0.3 mm

15 m

m separator

&

electrolyte

calculated experimental

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.

Li in a Fe (III)-rich

environment

Li containing

diamagnetic phase

Li in LiFeBO3

MRI of Electrodes Developing in situ Studies Modeling Delithiation of LiFePO4

Understanding Distribution of Phases Study of Electrochemical Processes

Understanding Hysteresis

upon d

egra

dation

Improving battery performance will be

driven by: