HIGHLIGHTS ON THE LATEST BATTERY TECHNOLOGY ACHIEVEMENTS & CHALLENGES

CEA tech - LITEN | PATOUX Sébastien

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� CEA Tech Grenoble

� Technology examples

� Conclusions

OUTLINE

Grenoble (France)

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The world’s most innovative research

institutions (Rank #1 in 2016 ; #2 in 2017)

CEA in brief: Technological strength-in-depthfrom atomic research to renewable energy

17 000 employees10 Research centers4B€ annual budget

700 priority patents filed / P.A.120 new high-tech start-up /companies created since 1984

639 patents /year (2016)

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Liten covers the entire value chain from materials to systems

MATERIALS

PROCESSES

COMPONENTS

SYSTEM INTEGRATION

DEMONSTRATION

FIRST PROTOTYPES

Impossible d’afficher l’image.

X rays Nanotomographyof ceramic cells

X rays Nanotomographyof ceramic cells

Powder for batteries

Powder for batteries

Fuel cell catalystFuel cell catalyst

Atomic scale modelling of

hybrides

Atomic scale modelling of

hybrides

Solar cellsSolar cellsBatteries cellsBatteries cells

PEMFC systemPEMFC system

Alsolen: 500 KW Fresnel Concentrated Solar Power Alsolen: 500 KW Fresnel Concentrated Solar Power

Integration of CEA technologies 15 KWh Li Battery + 25 kW PEMFC + 10,5 kg H2 ~350 kWh

Integration of CEA technologies 15 KWh Li Battery + 25 kW PEMFC + 10,5 kg H2 ~350 kWh

Solar charging station and micro gridSolar charging station and micro grid

Data analysis, modeling & simulationData analysis, modeling & simulation

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SMART GRIDTHERMAL SYSTEMS

POWDER METALLURGY

MICRO SOURCESLARGE SURFACE PRINTED

ELECTRONICS

NANO CHARACTERISATION

FUEL CELLS SOLAR PHOTOVOLTAICS

BIOMASS BATTERIESHYDROGEN

ELECTRIC VEHICLESBUILDING

Liten Institute Technology Platforms

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Material synthesis. Electrode coating. Cell andpack assembly. Mechanical and Electricaldesign. BMS architecture, Thermal modelling.Characterization. Abuse tolerance testing.

200 engineers and technicians ; >350 patents

5000 m² space (incl. 1000 m² of anhydrous labs)

60M€ investment since 2010

Industrial partners in France, Europe, Japan,Korea, US and Bolivia.

Focusing on lithium-ion battery development, the

platform develops end-to-end production systems for

wide-ranging applications. Unique in Europe, the

platform helps industry boost battery life, improve

reliability and cut costs.

BATTERY PLATFORM

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Characterization

& modeling

Electrodes

Components

Cells

Modules/packs

LCA/Recycling

OUR POSITIONNING

Abuse testing

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For more than 20 years !

MATERIALS SYNTHESIS : from g to Kg

- Organic materials

- Organic materials

- Water-based electrolyte (Li or Na ions)

- Paper-based separator

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Lab coater

(doctor blade)

L= 30 cm, l = 10 cm

Pre-pilot scale

(comma-bar)

L= 10 m, l = 14 cm

Pilot-scale

COATEMA (slot die)

L= 80 m, l = 200 mm

Pre-industrial scale

MEGTEC (slot die)

ELECTRODE COATING (including water-based and

solvent-free solutions)

10 – 250 mLThree-roll mill

High-shear disperser + ink ball-milling60 L

• COATING

• SLURRY PREPARATION

L= 300 m, l = 600 mm

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CELL ASSEMBLY AND TESTINGDry room ~ 1000 m²

Channels up to 700 V, 1000 A, 250 kW

- A stabilized design to investigate new chemistries,

- Capability to assemble prototypes in small series

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Electromobility application batteryPowerful and durableThe battery that gives the autonomy you need for your journey

Sensor batterySmall and resistantThe battery suitable for extreme external environments

Safety beacons batteryLong-life and reliableThe battery that ensures reliable communication everywhere

Medical ImplantSmall, safe & biocompatibleThe battery you can rely on for 10 years at body temperature

Ultra-thin batteryLight and discreteUltra light and ultra compact

Primary batteryLow-cost and storableThe battery that meets your short-time and sporadic energy needs

…and more

18650 standardFor representative benchmarkIndustrial reference

From 1 mAh to 70 Ah Li-ion cells, with on-demand packaging, architectures and designs

BATTERY CELL CUSTOMIZATION

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BATTERY DEVELOPMENT (MECHANIC, ELECTRIC AND

THERMAL DESIGNS)

- Battery Modules & pack assembly with e-management

- Semi automatic assembly with full components tracking

From kWh to MWh

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MODULE & PACKS – VARIOUS EXAMPLES

PHEV: HYPACK modules 7 kWh 400 V

E-bike: MOBILAB module

6 Ah 36 V

Fast charging e-Bus: MC2

module 70 kWh 700 VE-Boat ZERO CO2 PACK

16 kWh 400 V

EV: RC2 module 12 kWh 400 V

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EXPERIMENTATION with CEA battery system inside

End of bus line charge = 250kW in 5 min

27 kWh – 160 Wh/kg battery pack2 x 45 kWh battery packs

EOLAB hybrid concept car (7kWh,1L/100km)

Full Elec Power Pack (3 x 85 kWh)

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PV, controllable load banks, 45 kW grid

simulator, and battery emulators

EV charging station

Storage systems

(Batteries, H2, hybrid)

Houses

Energy software

intelligence

Smart micro-grid250kVA

80 kW PV and diesel

genset power production

Heat

microgrid

DEMONSTRATION IN SMART GRID

Technology selection & management optimization

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� CEA Tech Grenoble

� Technology examples

� Conclusions

OUTLINE

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Lithium-sulfur Sodium-ion Hybrid

SupercapacitorsNickel-zinc

Increase performances

• Energy

• Power

Decrease costs

• Economical

• Environmental

• Risks

Widen operational

conditions

• Temperature

• Flexibility• Durability

Metal-air

BEYOND conventional Li-ion batteries

Mg- and

Al-ion

Solid electrolytesOrganic Flexible Printed Composite

packagingRedox Flow

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TOWARDS LOW COST AND GREEN BATTERIES

� High and tunable electrochemical performancesPower : C-rate above 150C (charge in few seconds)

Energy : energy density x 2 (multi-redox reaction)

Tunable redox potential (chemical environment)

Various counter ions (Li+, Na+, K+, Mg2+,…)

� Low cost and sustainable electrode materialsLow cost precursors (biomass) / Green chemistry

Biodegradable / Recyclable

Less toxic (?)

Our building block : C,H, O, N, (S)

Cycle life of a ‘‘greener’’ Li-ion battery

based on organic materials

Poizot, Energy Env. Sci, 2011

Main issues :� Low electronic conductivity� Low cyclability (solubility in

electrolytes)

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EXAMPLE OF FULL ORGANIC BATTERY

Synthesis of positive and negative organic materials at pilot scale

Assembling full organic battery

� 1.2 V battery wih good cycle life. To be continued…

Iordache A., Delhorbe V., Bardet, M., Dubois L., Gutel T., Picard L. Appl. Mater. Interfaces , 2016

• Flexible

• Printed

• Colored

• Redox Flow

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POSITIONNING OF THE BATTERY TECHNOLOGIES

SAFETY

POWER

ENERGY

Supercapacitors

Li-Sulfur

Today’sLi-ion

ImprovedLi-ion

High Power Li-ion

KIC

Na-ion

Towards Solid State Batteries

Cycle life

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• Li-rich* materials : one of the best solution for cathode**

• Silicon based materials : the best solution for anode

• Li-metal anode should also beconsidered again

Li-rich/Si-C

Li-rich/Li

* Li-rich = Li1+xM1-xO2 (0<x<1/3 ; M = Mn, Ni,…)**New HEC (rocksalt…) are also investigated at CEA

HIGH ENERGY Li-ION BATTERIES

Silicon anodeLi-rich (Ni-rich) cathode

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High Energy Li-on roadmap

• Li-rich* materials : one of the best solution for cathode**

• Silicon based materials : the best solution for anode

• Li-metal anode should also beconsidered again

Li-rich/Si-C integration

Cell energy : 300Whkg-1

Configuration : 5S4P

Battery capacity : 16Ah

Battery voltage : 17V

Device rate : 8A (C/2)

Li-rich/Si-C

Li-rich/Li

* Li-rich = Li1+xM1-xO2 (0<x<1/3 ; M = Mn, Ni,…)**New HEC (rocksalt…) are also investigated at CEA

HIGH ENERGY Li-ION BATTERIES

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FROM LIQUID ELECTROLYTES…

• Ionic liquids• New solvents• Additives

• High flash point• Ionic liquids• Aqueous electrolyte• Redox shuttle• HF Scavenging• No gas generation

• New solvents• Additives• SEI promoting agents

• Low viscosity• High ionic conductivity• Aqueous electrolytes

HIGH POWER

HIGH VOLTAGE

HIGH T°C

LOW T°CSAFETY

+ Good wettability+ No metal dissolution

+ No current collector corrosion

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TO GELIFIED ELECTROLYTES

PCE (Lithium salt in succinonitrile)

� Alternative non-flammable electrolyte solvent

� Good ionic conductivity with 1M LiTFSi � 3.10-3 S/cm (RT)

� Operating temperature -20°C�150°C

� Non volatile � boiling point 266°C

� Low cost

� Good electrochemical stability (up to 5.5V)

Plastic Crystal based Electrolyte

Room T°C Room T°C

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AND SOLID STATE ELECTROLYTES

Inorganic Crystalline Materials(Perovskites, Garnets, Nasicon)

Inorganic Amorphous Materials(LiPON, glass sulfides…)

Solid polymers

with additives

to improve

Conductivity

(various options)

• 3 types of solid electrolytes :

� Eliminate flammable & toxic liquid electrolyte � Develop solid electrolyte

cathode

anode

� Low conductivity, high interface

resistance, processability issue at

the moment, but…

� Safer batteries and Higher

energy density expected :

• Less safety control embedded

• Unlock Li-metal anode

� New architecture, new processes

Understanding & fine characterizations (HRTEM, EELS, TOF-SIMS, 3D-FIB-SEM…)

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Sulfur cathode : 1675 mAh/gLi-ion : 100-250 mAh/g

Lithium anode : 3860 mAh/gLi-ion : 372 mAh/g

Li-S nominal voltage : 2.2 VLi-ion : 3.3 – 3.7 V

Material properties

• Liquid through solid electrolyte

• High energy in lightweight batteries

• Low cost and low environmental impact

Challenges

� Sulfur dissolution

� Polysulfide dissolution� � Changes in positive electrode morphology,

pulverization� � Polysulfide shuttle

Nucleophilic polysulfides� Restricted electrolyte choice

Lithium metal corrosion (electrolyte, Li2Sn)

� Lithium cyclability, foam, dendrites

� Insulating and insoluble Li2S/S8� Electrode passivation� High carbon content

LITHIUM/SULFUR BATTERIES

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Sulfur cathode : 1675 mAh/gLi-ion : 100-250 mAh/g

Lithium anode : 3860 mAh/gLi-ion : 372 mAh/g

Li-S nominal voltage : 2.2 VLi-ion : 3.3 – 3.7 V

Material properties

Li/S roadmapSeveral strategies

+ + =

First cylindrical hard packaging cells (AA design)

• A compromise

between Energy and

Cycle life.

• Not so good in Wh/L

LITHIUM/SULFUR BATTERIES

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NA-ION : AN ALTERNATIVE TO THE

LI-ION TECHNOLOGY ?

• Design and development of new materials for Na-ion

• Material scale-up (kg)

• « Product » approach (↗ TRL)

• Battery Platform with control of the whole value chain

The 6th most abundantelement in the Earth Crust(33th for Lithium)

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NA-ION : AN ALTERNATIVE TO THE

LI-ION TECHNOLOGY ?

24 cells 50125, 960Wh, 48V

► High performances in terms

of Power & Cycle life.

► Ready for making the first

demonstrators (module & pack)

Backup stationary application

(UPS).

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HYBRID STORAGE SYSTEM : LI-ION CAPACITOR

Li-ion capacitor

++++++++

-

-

-

-

-

-

e-

+-Li+

Li+

Li+Li+

Li+Li+

Li-ion battery EDLCLIC

Graphite Activatedcarbon

EDLC

Li-ion battery

Pack power density

Pack energydensity

Cycleability(>5000 @ 100%DoD

Cost(TCO vs cycle)

Low T (<-10°C)

Safety

++++++++

--------

-

-

-

-

-

-Activatedcarbon

Activatedcarbon

+

+

+

+

+

+

+-

Graphite Insertion material

+-e-

Li+ Li+

Li+Li+

Li+

Li+

Li+Li+

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0 50 100 150 200 250 300 3500,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

0 20 40 60 80 100 120140 160 1800,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

Umax = 1,75V

Umax = 3,5V

U (

V)

time (h)

Umax/2 = 1,35V

U (

V)

time (h)

Umax = 2,7V

Cost efficiency

Improvement of device safety

POTASSIUM-ION CAPACITOR SYSTEM (KIC)Key point of the technology

Presence of potassium

Aluminum current collector

Compatibility with acetonitrile

++++++++

PF6-

K+ K+

K+ K+

K+ K+

Graphite /KPF6 1M (ACN)/Activated carbon

No signature of SEI formation

No risk of potassium plating

PF6-

PF6-

Hybrid KiC

Conventional EDLC

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KIC FULL CELL TESTING

Device ageing at RT High rate performances

Excellent stability at high charge/discharge rate (>100,000 cycles)

Excellent performances at high rates (95% retention at 300D; 86% at 400D)

Low heat elevation (+1°C at 400D)

7.4 Wh.kg-1 and 3.4 kW.kg-1 in 18650 cell

Prelimirary results ; improvement on going (patents filling)

Vol

tage

(V

)

Cell capacity (mAh)

18650 cell

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� CEA Tech Grenoble

� Technology examples

� Conclusions

OUTLINE

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MAIN TARGETS

• New materials for anode, cathode,

electrolyte, packaging,…

• New processes (printing, extrusion, RTM,

flame spray or laser pyrolysis…)

• Solid state batteries (safety)

• Lithium metal control (structuration and

protection)

• New architectures (3D, conformable,…)

• Various battery technologies

• Hybridation with fuel cells, solar panels,

wind turbines…

Commissariat à l’énergie atomique et aux énergies alternatives

Centre de Grenoble | 38054 GRENOBLE Cedex 09

T. +33 (0)4 38 78 29 20 | sebastien.patoux@cea.fr

Etablissement public à caractère industriel et commercial | RCS Paris B 775 685 019

Direction de la Recherche TechnologiqueLiten

Thank youfor your

attention !

Contact : sebastien.patoux@cea.fr