JOINT CENTER FORENERGY STORAGE RESEARCH

Next Generation Energy Storage

George CrabtreeDirector, JCESR

Argonne National LaboratoryUniversity of Illinois at Chicago

OutlineThe Energy Storage Challenge: Transportation and the Electricity Grid

Beyond Lithium-ion ConceptsFour Proof of Principal Prototypes

NY-BEST Energy Storage ConferenceSyracuse, NY

October 20, 2016

Automated Mobility Services Require Cheaper, Higher Performing Batteries Personal Electronics

Lithium-ion batteries enabledthe personal electronics revolution

Forever changed the way we interact with people and information

Transportation: $20K electric cars Diversity transportation fuelsLower carbon emissionsReduce energy useLower operating costs

Grid-scale electricity storageWidespread deployment of wind and solar

Enhance reliability, flexibility, resilienceUncouple instantaneous generation

from instantaneous demand

~ 2% of US energyPersonal electronics

28% of US energyTransportation

39% of US energyElectricity grid

TRA

NS

PO

RTA

TIO

NG

RID

$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: Beyond Lithium-ion Batteries for Cars and the Grid Vision

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

MissionDeliver 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 transformative 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

JCESR’s Beyond Lithium-ion Concepts

Multivalent Intercalation

Chemical Transformation

Replace monovalent Li+ with di- or tri-valent ions: Mg++, Ca++, Al+++, . . .

Double or triple capacity

Replace solid electrodes with liquid organic solutions or suspensions:

lower cost, higher capacity, greater flexibility

Macromolecular Organic Redox Flow

Lithium-ion “Rocking Chair”Li+ cycles between anode and cathode,

storing and releasing energy

Replace intercalation with high energy chemical reaction: Li-S, Li-O, Na-S, . . .

e

Li+Li metal anode

Sulfurcathode

Li+

e

Metal oxide

cathode

Graphite anode Liquid

organic electrolyte

Mg++

e

Metal oxide

cathode

Mg metalanode Liquid

organic electrolyte

Liquid organic

electrolyte

Redox Active Colloid

Redox Active Polymer

Redox Active Oligomer

Redox Active Molecule

Proof-of-concept

Prototypes Transportation

Grid

Organic Redox Flow

TE modeling

Genome

Synthesis

EDL

MaterialsComponentsIntegration

Li-Sulfur StationaryLi-O

Li-S Flow

Four Prototype Targets

Air-Breathing Aqueous

Sulfur

Science-Driven Outcomes

MultivalentMg++, . . .

Science-Driven Outcomes

Final Prototype Targets Selected Jan 2016

JCESR Spins Out Two Startups

Nitash Balsara, Alex Teran and Joe DeSimone (UNC)Inorganic-polymer hybrids for Li anode batteriesVillaluenga et al, PNAS 113, 52, (2015)

Robin Johnston, Michel Fouré, Brett Helms and Peter Frischmann

Lightweight energy storage for the electrification of flight

Li et al, Nano Lett. 15, 5724 (2015)Best All-around Team

Bay Area I-Corps competition

Blue Current

Sepion

Engaging the private sectorTraining next generation entrepreneurs

Building JCESR relationships

Further ReadingJonathan Walker and Charlie Johnson, Peak Car Ownership: The Market Opportunity of Electric Automated Mobility Services, Rocky Mountain Institute, 2016, http://www.rmi.org/peak_car_ownership.

Jeffery B. Greenblatt and Samveg Saxena, Autonomous taxis could greatly reduce greenhouse-gas emissions of US light-duty vehicles, Nature Climate Change 5, 860 (2015).

George Crabtree, Elizabeth Kocs and Lynn Trahey, The Storage Frontier: Lithium-ion Batteries and Beyond, MRS Bulletin 40, 1067 (2015).

Why Energy Storage May Be the Most Important Technology in the World Right NowForbes Apr 1, 2016

Frontiers of EnergyNature Energy Jan 11, 2016Ten experts, including JCESR’s George Crabtree, share their vision of coming energy challenges

Perspective: The Energy Storage RevolutionNature Oct 28, 2015How next-generation storage can change the car and the grid

Lithium Batteries: To the Limits of LithiumNature Oct 28, 2015

Why We Need A Revolution in Energy StoragePBS Jan 5, 2016

Supplemental Slides

Li-ion

Li-ion

Development of Lithium Batteries

1970-2015

Gravim

etric Energy Density (W.h/kg)

Cost

(US$

/kW

. h)

3000

2000

1000

0

300

200

100

0

Year

20151970 1980 1990 2000 2010

Ni-MHNi-Cd

1971Conceptualization

1991Commercialization

Crabtree, Kocs, Trahey, MRS Bulletin 40, 1067 (2015)

Lessons from Lithium-ion Batteries

Long incubation period

Lithium-ion battery of 1991looked nothing like

the 1970s vision

Many (most) good ideas fail

Multiple paths forward are critical

20 year

incubation

JCESR Creates a New Paradigm for Battery R&D

Multivalent Intercalation

Chemical Transformation

Non-Aqueous Redox Flow

CR

OS

SC

UTT

ING

S

CIE

NC

E

SystemsAnalysis and Translation

Cell Designand

Prototyping

Commercial Deployment

Battery Design

Research Prototyping

Manufacturing Collaboration

MATERIALSPROJECT

Sprints

Discovery Science++

TECHNO-ECONOMIC MODELING“Building battery systems on the computer”

ELECTROCHEMICAL DISCOVERY LAB

https://www.youtube.com/watch?v=wEzsKJwYjDQ

Focus exclusively on beyond lithium ion

A single highly interactive organization

JCESR Team

20 Institutional Partners, 180-200 Researchers

Multivalent Intercalation

One working example: Mg++ in Chevrel phase Mo6S8, Aurbach et al (2000), Levi et al (2006)

ConceptReplace Li+ with Mg++, Ca++, Zn++Advantage: double the energy per ion transfer

++

e

MV metalanode

Intercalation cathode

Organic electrolyte

Mg++

Ca++

Zn++

Why is progress so slow?Too many candidates, too few winners

Inadequate fundamental understanding for rational design

ChallengesMany cathodes operate at low voltage low energy densityDivalent ions move slowly in cathode slow charge, dischargeElectrolytes decompose at desirable cathode voltagesAnode surface degradation on plating and stripping

Promising Mg Cathodes

Mo6S8 Cr2S4

Ti2S4

Cr2O4

Ni2O4

Co2O4

Mn2O4

ps-Mn2O4

ps-Co2O4

BL-V2O5

Where we are going

Where we are Diameter ~ mobility

Dotted lines: cathode-only energy density

Trends

Voltage: Oxides higher than sulfides

Capacity: Oxides higher than sulfides

Mobility: Sulfides higher than oxides

Synthesis: Sulfides easier than oxides

Lithium-Sulfur Challenges e

Li+Li metal anode

Sulfurcathode

S8 (s) + 16 Li ↔ 8 Li2S (s)

U = 2.2 V vs Li

S Li2SLi2Sx

Li2S8

Li2S6 Li2S4

Li2S?Sx

2-

Polysulfides: Li2Sx

• soluble in electrolyte• migrate to anode • react with Li precipitate • depletes Li and S • limits cycle life

Li-electrolyte side reactionDepletes Li and electrolyteLimits cyclesConventional fix: large excess of Li and electrolyte

Li dendrite growth• cycling roughens Li surface• dendrites form and grow • break off to deplete Li• grow across electrolyte to

short cathode

Li dendrite

Plating

JCESRmembrane in contact with Li anode surfaceMaintain coherent interface as Li strips and plates through membrane

JCESR • “lean” electrolyte• sparing solvation• solvates Li and anion, but

not polysulfides

JCESR Protective membrane

• blocks electrolyte• allows Li conduction

anode cathodeelectrolyte

Functionalized grapheneoxide membrane

JCESR Prototypes Constructed and Tested Push State-of-the-Art

JCESR today: 1 Ah Li/S cell (6 layers)• 270% excess Li• 1.7 mLElectrolyte/gSulfur lean electrolyte• > 4.5 mAh/cm2 areal charge density in cathode

JCESR targets • < 100% excess Li • 1 mLElectrolyte/gSulfur• > 8 mAh/cm2

1 M LiTFSI, 0.2 M LiNO3DOL:DME (v/v)

Chen et al., in prep (2016)

Rese

arch

Indu

stry

SO

A

JCES

R to

day

JCES

R ta

rget

JCES

R to

day

JCES

R ta

rget

Eroglu et al., J. Electrochem. Soc., 162(6) A982 (2015)

ActiveMaterial

US$/kg Ah/kg US$/kAh

LiCoO2 40.0 136.92 138.7

Graphite 10.0 371.90 26.9

Li 66.4 3861.26 17.20

Na 2.0 1165.78 1.72

S 0.20 1671.67 0.12

Air-Breathing Aqueous Sulfur Flow BatteryTeam: MIT (Chiang, Brushett), LBNL (Helms), Waterloo (Nazar)

16 TWh of Li/S batteries

~ 4M cubic meters of sulfur from oil sands Fort McMurray, Alberta

• Ultralow $/Ah cost of sulfur • High solubility in water 4X the energy density

of V-redox solutions

Wind farms baseload powerSeasonal energy storage, summer winter

Can inexpensive, large scale electrochemical storage compete

with pumped hydro and compressed air?

T-E model includes everything including profit marginPHS = pumped hydroelectric storage

CAES = compressed air energy storage

Where Aqueous Sulfur fits in the world of grid storage

100-300h storage to turn a windfarm into baseload power

Testing Air-Breathing Aqueous S Flow BatteryFull cell reaction

2Na2S + O2↑+ 2H2SO4⇄ 2S + 2Na2SO4 + 2H2O

H2OSn

2-

Na+

OH-

(+) Positive (-) Negative

A-io

n co

nduc

ting

solid

ele

ctro

lyte

O2

Na+

e-

O2H+

Na+

SO42-

O2 + 4H+ + 4e-

2H2OS2- S + 2e-

(discharge)

Pump

Cell

Reservoirs

In 2014, JCESR Introduced the Concept of Macromolecular-based Redox Electrolytes . . .

Elec

trod

e Pa

rtic

le S

ize

RAC105-109

redox unitsColloid

RAP10 -1000

redox unitPolymer

RAO2 -10

redox unitsOligomer

RAM1 redox unitMolecule

AdvantagesInexpensiveRecyclableDesign for• Solubility• Stability• Activity• Size selectivity

. . . and the field gains momentum as others follow our lead . . . Synthesis and characterization of TEMPO- and viologen-polymers for water-based redox-flow batteries, Polym. Chem., 6, 7801-7811 (2015)

Poly(TEMPO)/Zinc Hybrid-Flow Battery: A Novel, Green, High Voltage, and Safe Energy Storage System, Adv. Mater. 28, 2238–2243 (2016)

Poly(boron-dipyrromethene)—A Redox-Active Polymer Class for Polymer Redox-Flow Batteries, Chem. Mater., Article ASAP Publication Date (Web): May 6, 2016

CelgardInexpensiveoff the shelf

Polymer Intrinsic Microporous (PIM) membranes developed in JCESR for Li-S

polysulfide selectivityTunable pore size ~ 1 nm

Li et al., Nano Letters, 15, 5724 (2015)

JCESR’s Macromolecular Organic Flow Cell Directions

0 2 4 6 80.5

1.0

1.5

2.0

2.5

Volta

ge (V

)

Time (Hour)

Full cells of all four types routinely cycled

Target for next 18 monthsPrimary: RAO-PIM for cost target

Secondary: RAP-Celgard for cost -performance comparison

based on TE modeling