Research to Enable Next-Gen Batteries

An Overview December 2, 2014

Fairbanks, Alaska

Jeff Chamberlain Deputy Director, JCESR

Argonne National Laboratory

Overview of this discussion

Introduction to Argonne Battery Program – Lithium Ion Research at ANL – Beyond Lithium Ion – Joint Center for Energy Storage Research

Discussion of Grid Storage opportunity and complexity

State of Battery Development for Grid

Plea for collaboration, on both research and adoption

2

The national need for energy storage is driven by: - Security - Economy - Environment

The projected doubling of world energy consumption in 50 years. A growing demand for low- or zero-emission energy sources. Part of the solution entails the transformation of our transportation and stationary storage technologies…

3

Energy flow chart shows relative size of primary energy resources and end uses in U.S.

Economic Drivers are Enormous: transportation

5% penetration of PHEVs = $18B in annual revenue, for battery packs alone

(assuming current estimates of $7500/pack)

Source: Takeshita Report, 2008

Economic Drivers are Enormous: grid

Concerns about global climate change are growing

Example: Market is growing for electric vehicles http://energy.gov/articles/visualizing-electric-vehicle-sales

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Adoption rates: PHEV+EV compared to Prius

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Month to month vehicle sales since introduction

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Example: Policy for the grid will drive adoption

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California Passes Huge Grid Energy Storage Mandate CPUC passes controversial mandate for 1.3 gigawatts of batteries, grid storage by 2020 Jeff St. John October 17, 2013 GreenTechMedia

Breaking: SCE Announces Winners of Energy Storage Contracts Worth 250MW Stem, AES, Ice Energy, NRG Energy and Advanced Microgrid Solutions garner more than 250 megawatts in energy storage awards. Eric Wesoff, Jeff St. John November 5, 2014 GreenTechMedia

Revolution in Energy?

Grid of the Past

Modern energy system is increasingly complex

Grid of the Future: Requires Energy Storage

Modern energy system is increasingly complex

Grid of the Future: Requires Energy Storage

Modern energy system is increasingly complex

Africa

India

South America

Wind conversion has variance

Electricity from renewables cannot be produced on-demand

Storage is required to mitigate variation

Daily profiles from wind power in Tehachapi CA (ISO California) show wide variance day-to-day and hour-hour

(Chem Reviews, Yang, PNNL)

Solar conversion has variance

Electricity from renewables cannot be produced on-demand

Storage is required to mitigate variation

5 MW PV power over 6 days in Spain (AES)

(Chem Reviews, Yang, PNNL)

Need for storage goes beyond renewables

Storage needs span: Production, high-power (short time) swings, industrial, commercial, and residential application

(Chem Reviews, Yang, PNNL)

Electric Energy Storage (EES) Technology Options for Grid Applications

Elec

tric

al e

nerg

y

Electrical charges: capacitors

Potential energy:

pump hydro, compress air,

Kinetic energy: flywheels

Chemical energy: batteries

Direct

Storage in

charges

Indirect

storage via

energy conversion

Beacon power

Technology options dictated by storage needs

(Chem Reviews, Yang, PNNL)

Cost dominates the technology decision

(Chem Reviews, Yang, PNNL)

Storage Projects in the U.S.

Source: Electricity Storage Association, PJM Interconnection Data from DOE’s Global Energy Storage Database http://www.energystorageexchange.org/projects

13 different chemistries, technologies

Discharge

Lithium Ion Battery

Anode Cathode

e-

Charge

Electrolyte

A Chemical Reaction in your Pocket

Battery materials research challenges: Spacial and Temporal Phenomena

29

ZS

Solvation Shell Formation and

Evolution

Li Solvation Shell Dynamics under E field

SEIs Formation

and Evolution

Cathode intercalation

Dynamics, PTs, Cathode

Fracture

Stress Propagation, Interaction, Dislocation,

Fracture

Cyclical Degradation of Electrode and SEI Material

pm

nm

µm

mm

cm

fs ps ns µs ms s h

time

leng

th

1st cycleirreversiblecapacity loss

287

352

0

1

2

3

4

5

6

0 50 100 150 200 250 300 350 400

Volta

ge v

s. L

i (V)

Capacity (mAh/g)

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mA

h/g)

chargedischarge

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mA

h/g)

chargedischargechargedischarge

287

352Li1-xMn0.5Ni0.5O2

168 mAh/g

Li2-xMnO3-x/2

152 mAh/g

First cycle, RT5.0 to 2.0 VC/24 ratei = 0.16 mA

Electrolyteoxidation

287

352

287

352Li1-xMn0.5Ni0.5O2

168 mAh/g

Li2-xMnO3-x/2

152 mAh/g

First cycle, RT5.0 to 2.0 VC/24 ratei = 0.16 mA

Electrolyteoxidation

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mAh

/g)

chargedischarge

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mAh

/g)

chargedischarge

-Li2O 1st cycleirreversiblecapacity loss

287

352

0

1

2

3

4

5

6

0 50 100 150 200 250 300 350 400

Volta

ge v

s. L

i (V)

Capacity (mAh/g)

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mA

h/g)

chargedischarge

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mA

h/g)

chargedischargechargedischarge

287

352Li1-xMn0.5Ni0.5O2

168 mAh/g

Li2-xMnO3-x/2

152 mAh/g

First cycle, RT5.0 to 2.0 VC/24 ratei = 0.16 mA

Electrolyteoxidation

287

352

287

352Li1-xMn0.5Ni0.5O2

168 mAh/g

Li2-xMnO3-x/2

152 mAh/g

First cycle, RT5.0 to 2.0 VC/24 ratei = 0.16 mA

Electrolyteoxidation

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mAh

/g)

chargedischarge

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mAh

/g)

chargedischarge

1st cycleirreversiblecapacity loss

287

352

0

1

2

3

4

5

6

0 50 100 150 200 250 300 350 400

Volta

ge v

s. L

i (V)

Capacity (mAh/g)

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mA

h/g)

chargedischarge

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mA

h/g)

chargedischargechargedischarge

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mA

h/g)

chargedischargechargedischarge

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mA

h/g)

chargedischargechargedischargechargedischargechargedischarge

287

352Li1-xMn0.5Ni0.5O2

168 mAh/g

Li2-xMnO3-x/2

152 mAh/g

First cycle, RT5.0 to 2.0 VC/24 ratei = 0.16 mA

Electrolyteoxidation

287

352

287

352Li1-xMn0.5Ni0.5O2

168 mAh/g

Li2-xMnO3-x/2

152 mAh/g

First cycle, RT5.0 to 2.0 VC/24 ratei = 0.16 mA

Electrolyteoxidation

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mAh

/g)

chargedischarge

254200

250

300

350

400

1 2 3 4 5 6 7 8 9 10 11Cycle No.

Cap

acity

(mAh

/g)

chargedischarge

-Li2O

Theoretical capacity of LiMn0.5Ni0.5O2 Component: 184 mAh/g Theoretical capacity of Li2MnO3 Component: 158 mAh/g Theoretical charge capacity (total): 342 mAh/g Coulombic efficiency: 82% (1st cycle); >99% (10th cycle) Capacity (10th cycle): 254 mAh/g

Electrochemistry of a Li/0.3Li2MnO3•0.7LiMn0.5Ni0.5O2 Cell

HAADF-STEM

Li2MnO3

Li1.2Co0.4Mn0.4O2

32

33

Li-Ion Batteries: Anode Materials

34

Carbon • Graphite: <100 mV vs. Li0

• Moderate capacity (372 mAh/g) • Highly reactive, surface protection necessary

Metal Oxides • Li4Ti5O12 (Li[Li1/3Ti5/3]O4) Spinel: 1.5 V vs. Li0 • Low capacity (175 mAh/g) • Very high rate capability • Stable in nanoparticulate form

Metals, Semi-metals and Intermetallic Compounds • Al, Si, CoSn, Cu6Sn5: <0.5 V vs. Li0 • High gravimetric/volumetric capacities (1000-4000 mAh/g) • Large volume expansion on reaction with lithium • Reactive, surface protection required • Greatest opportunity and challenge

LiC6

LiAl

•

• •

Li7Ti5O12

Silicon particles uniformly embedded inside graphene layers

Si-Graphene composites prepared through Gas Phase Deposition

Cell Data

Half Cell

Si-Graphene with LMR-NMC

Si-Graphene possesses reversible capacity of 1100 mAh/g in 100 cycles

340 Wh/Kg energy density could be achieved by this chemistry*

-400

100

600

1100

1600

2100

2600

0

300

600

900

1200

1500

0 20 40 60 80 100

Cap

acity

, mA

h/g

Cycle

Si-Graphene Composites

Si Electrode

0

200

400

600

800

1000

1200

1400

1600

0 10 20 30 40 50 60

Cap

acity

, mA

h/g

Cycle

Discharge

Charge

C/3

C/20

*Based on Argonne's Battery Design Model

Silicon on 3-D Archtectures: Substrates: Copper foam synthesis

The porosity, thickness, and surface roughness of homemade foams is highly tunable. Commercial foams, however, offer the ease of reproducibility. More commercial vendors will be sought in order to have varying porosities.

(left) Electrodeposited Cu foams with same Sn deposition performed on each. (A) 1mM chloride concentration in Cu bath, (B) 4 mM chloride concentration in Cu bath

(right) Calendered commercial foams (CircuitFoil) before and after calendaring to 100 μm.

High Voltage Redox Shuttle for Protection of 5V Cathode

Argonne’s Materials Engineering Research Facility

Argonne’s Materials Engineering Research Facility

Conference/Break Room

High Bays

Unfinished Space Unfinished Space Process R&D Lab Process Scale-up Lab

Analytical Lab

Cell Fabrication Facility (CFF)

41

The CFF was established by DOE-EERE, Vehicle Technologies Program, to fabricate commercial-grade sealed cells to facilitate the performance & life testing of promising advanced materials and cell chemistries developed on the ABR Program

– Fabrication equipment housed in a new dry-room facility built for this purpose

– Semi-automated equipment capable of coating, calendaring, & slitting electrodes; fabricating multi-electrode stacked pouch cells; & fabricating 18650 cylindrical cells

ARRA funding used to procure cell formation, test, and characterization equipment

Battery Test Laboratory

• New PC-based control & data acquisition system

• New software (PC compatible)

• New environmental chambers for testing cells and modules

Conduct independent performance & life tests: • DOE/USABC deliverables • Non-DOE supported

technologies • ABR Program cells Utilize life test data to develop life prediction models for different technologies

New Post-Test Analysis Facility (PTF)

43

Linked to & operated in a manner similar to the battery test facility

ARRA funding was used to establish a new integrated post-test analysis facility incorporating a variety of teardown & diagnostic capabilities:

Joint Center for Energy Storage Research JCESR is a consortium of institutions led by Argonne

What is the Joint Center for Energy Storage Research?

Mission, team, plan of action

What are we doing? Computation, materials discovery, characterization

Why a team?

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TRA

NS

PO

RTA

TIO

N

GR

ID

$100/kWh

400 Wh/kg 400 Wh/L

800 W/kg 800 W/L

1000 cycles

80% DoD C/5

15 yr calendar life

EUCAR

$100/kWh

95% round-trip efficiency at C/5 rate

7000 cycles C/5

20 yr calendar life

Safety equivalent to a natural gas turbine

JCESR Has Transformative Goals Vision

Transform transportation and the electricity grid with high performance, low cost energy storage

Mission: 5-5-5 Deliver electrical energy storage with five times the energy

density and one-fifth the cost of today’s commercial batteries within five years

Legacies •A library of the fundamental science of the materials and phenomena of energy storage at atomic and molecular levels

•Two prototypes, one for transportation and one for the electricity grid, that, when scaled up to manufacturing, have the potential to meet JCESR’s 5-5-5 goals

•A new paradigm for battery R&D that integrates discovery science, battery design, research prototyping and manufacturing collaboration in a single highly interactive organization

Multivalent Intercalation

Chemical Transformation

Non-Aqueous Redox Flow

CR

OS

SC

UTI

NG

S

CIE

NC

E

Systems Analysis and Translation

Cell Design and

Prototyping

Commercial Deployment

Top-down Challenges

Bottom-up Research

Battery Design

Research Prototyping

Manufacturing Collaboration

MATERIALS GENOME

TDTs

Discovery Science

JCESR Creates a New Paradigm for Battery R&D

47

The JCESR Partner Team

National Laboratories Argonne

Lawrence Berkeley

Sandia

SLAC

Pacific Northwest

Discovery Science Battery Design

Research Prototypes

Manufacturing Collaboration

Universities University of Illinois at Chicago

University of Illinois at Urbana-Champaign

Northwestern University

University of Chicago

University of Michigan

Faculty from MIT, University of Waterloo, Harvard, Notre Dame

Private Sector Johnson Controls (JCI)

Dow

Applied Materials

Clean Energy Trust

Multivalent Intercalation

Chemical Transformation

Non-Aqueous Redox Flow

CR

OS

SC

UTI

NG

S

CIE

NC

E

Systems Analysis and Translation

Cell Design and

Prototyping

Commercial Deployment

The Pair Distribution Function, G(r) - A weighted histogram of atom-atom distances

rmax

Atomistic structure models

e.g. real space Rietveld, RMC

Peak Position Atomic distances Peak Area Coordination number Peak Width Disorder Peak rmax Particle size, coherence

48

49

Complementarity of x-ray scattering experiments and computational modeling

Key advantages of combined experimental-computational approach: 1. Experimental data used to calibrate

the inter-atomic potential used in computations

2. Computational models provide additional chemical details

S Lapidas, K Chapman, P Chupas (ANL) K Perrson, N Rajput (LBNL)

Genomic Approach to Computational Materials Discovery

Genomic Approach to Computational Materials Discovery

Non-Aqueous Redox Flow Cell Design PATH TO GRID STORAGE AT <$100/KWH

10x energy density of benchmark flow batteries ($250-450/kWh) Low cost materials Simplified system architecture Scalable low-cost manufacturing

52 May contain trade secrets or commercial or financial information that is privileged or confidential and exempt from public disclosure.

• Non-uniform flow (viscous fingering) • Contact line pinning • Beneficial to increase slip

1st Gen GIFCell

Active Material

*Active Material: 2.5M (of S) in the form of Li2S8, 0.5M LiTFSI, 1wt% LiNO3 in TEG-DME, 0.5vol% carbon

Evolution of GIFCell

54

Process flow of design & cost battery model

• Bottom-up performance and cost model • Account for each component necessary to make functioning battery • Captures manufacturing cost by building the facility for each battery

• Builds upon BatPaC: Peer-reviewed Li-ion model www.cse.anl.gov/batpac

May contain trade secrets or commercial or financial information that is privileged or confidential and exempt from public disclosure.

Materials in a single layer of Li/O2 cell

55

50% excess

Negative electrode Lithium-metal, 50% excess Solid ceramic electrolyte Hermetic, long-lived seal

Positive electrode Carbon-like porous felt Liquid electrolyte 60 vol% Li2O2 at discharge

Flow-field/positive current collector 0.3 MPaa Air: corrugated Al foil

● Sized for 30 kPa pressure drop ● Optimistically assume 20 um thickness

Pure O2: standard battery Al foil ● Porosity of electrode is enough

May contain trade secrets or commercial or financial information that is privileged or confidential and exempt from public disclosure.

Multiple scales and approaches to design

56

Electrode Sizing

Pack & System Closed system Open system

Li-O2 Chemistry

Cell & Module 50% excess Lithium

May contain trade secrets or commercial or financial information that is privileged or confidential and exempt from public disclosure.

57

50 kWh Designs: Li/O2 open scales poorly with energy

Li-air pack will have increased cost and volume associated with it

80 kWnet, 50 kWhuse 360 V battery May contain trade secrets or commercial or financial information that is privileged or confidential and exempt from public disclosure.

Just as the U.S. draws strength from it’s melting pot, so does the JCESR team of scientists and engineers

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Molecular discovery and design is required, but without prototyping, not enough is known

N

N 2e-

N

N

Li+2Li+

BF4-

PF6-

BETI-

Via collaborative computational, electrochemical, & synthetic efforts…

Unexpected anion sensitivity limits electrolyte selection

10x performance difference!

JCESR example of research across spectrum

Storage Projects in the U.S.

Source: Electricity Storage Association, PJM Interconnection Data from DOE’s Global Energy Storage Database http://www.energystorageexchange.org/projects

13 different chemistries, technologies

ANL’s capabilities span R&D, but we need help

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Research Development

Demonstration Deployment