Advances of Li-ion use in industrial applications

Anne de Guibert

12 March 2013

2

Content

1

2

3

4

5

6

Deployment of small Li-ion batteries from the origin (1991)

Technical issues and products development

Specialty applications (space, aviation)

Mobility markets

ESS

Conclusions

Why lithium-ion for industrial applications ?

Energy is three times lead-acid, the reference of industrialbatteries

It can be the best for almost all industrial applications withrespect to many criteria (not all at the same time): energy,power, life, cold environment, high temperature, vibrations…

Different « sub-systems » are possible according to the choice ofthe solid electrode materials and electrolyte which allow tochoose the system according to the priorities of the application

3

Comparison of industrial battery performances (cell level)

C/100

C/10

C

10C

100C

1

10

100

1000

10 000

100 000

0 20 40 60 80 100 120 140 160 180 200

Energy [Wh/kg]

Po

wer

[W/k

g]

Super capacitor

Ni-MH

Ni-Cd

High Power Li-ion (VLP)

Medium Power Li-ion (VLM)

High energy Li-ion (VLE)

Very-high power Li-ion (VLV)

AgO-Zn

Ultra-high power (VLU)

Ragone diagram

StandardLead-Acid

4

5

1 Deployment of small Li-ion batteries from theorigin (1991)

Mr Morita’s vision

Sony’s boss wished lighter camcorders not larger thanhis hand and with more autonomy

> His laboratories found the practical method using reversibleinsertion of lithium in carbon, much better than Li metalcells who led Moli to bankruptcy

> Sony bought the Goudenough patent on LiCoO2

> At the same time 3 major patents were filed by Asahi Kaseion micro-porous separators and cells

The first cells were 18650 using coke as negativematerial and LiCoO2 as positive material. They had acapacity of 900 mAh.

6

State-of-the-art of the best portable cells

The 18650 cell of 2012 reaches a capacity of 3.4 Ah (tocompare with 0.9 Ah twenty years ago)

20 years ago, I achieved 1200 cycles at 100% dod. This isno longer an objective.

Progress for high power applications: Sony Fortelion cell

7

Specific energy: 266 Wh/kg; positive NCANegative graphite (no silicon); made byPanasonicNext step: 3.6 Ah

Capacity 1.1 Ah : high power cellpositive blend of LFPsNegative graphite blendElectrolyte with additives to stabilize SEI

8-10 % volume growthper year in the nextyears

Price continues todecrease slowly

A mix of cylindricalcells (18650), prismatichard case and pouchcells according tocountry and market

8

Li-ion portable cells market growth

Use of progress made by portable cells

Progress made by portable cells pave the way onadvanced materials, electrodes and cells manufacturingalso usable in industrial cells:

> High energy materials

> Use of blends as electrode materials (build efficient blends)

> Electrodes manufacturing processes

> Cell design

But nothing more available for large high voltage batteries

9

10

2 Technical issues and products development

Criteria priorities in portable and industrial markets

Portable applications (small batt.)

1. Highest volumetric and specificenergy

2. Low cost

Life just sufficient (1-3 years)

Safety issue is easily solved aslong as manufacturing is correct

Industrial applications (large batt.)

1. Low cost (cell and system)

1. Safety of large cells and highvoltage batteries

1. Long life (cycling, calendar) andno maintenance

2. Several criteria according tomarket segment (fast charge, lowtemperature, high temperature,microcycling…)

Knowledge of system status: SOC,SOH, model)

11

Major differences in the added value chain

12

Raw materials Functionalizedmaterials

Components Cell Battery Application

RecyclingCo, Ni, Mn,

Al, Fe, Pb, Cd

Applications

Standby- safety- ESS- telecom

traction- HEV, EV

Battery pack- BMS, CSC

(CellSupervisionController)

- Interfaceselectric,thermal,mechanics

Geometrycylindricalprismaticpouch

Canvalvecircuit

breaker

ElectrodesCurrentcollectors

Positive : LCONCA, NMC, LFPLMO, LMP, …Negative : C, LTO,Si/C, Sn/C,…Binders: PVDF,SBR, CMC, PAAc,PI…ElectrolyteSeparator

LiFe, Mn, Co, NiAl, CuC, TiSi, Sn

Common concern portable/industrial Important specific new aspects for industrial

Industrial batteries step by step

1. Materials, electrodes

2. Cells

3. Battery hardware:

> mechanics

> thermal management

> safety from mechanical devices

4. Electronics

> Integration of algorithms

> Cell balancing

> Safety at system level

13

14

1. Materials: domains of excellence of Li-ion subsystems

Li-ionchemistries

C/NCAC/LiCoO2

C/NMC(s)

Newgenerationsfor >0 & <0 C/LiFePO4 and

other LiMPO4

C/LiFePO4 andother LiMPO4

Li4Ti5O12/NMC

C/LMO

C/LiFePO4& LiMPO4

Longest life

Lowest cost

Easiest to manufacture

Higher energyexpected

Best chargeability

Best trade-off

Highest stability

15

1. Potential uses in industrial applications: cost, safety, energy

Li-ionchemistries

C/NCAC/LiCoO2

C/NMC(s)

Newgenerationsfor >0 & <0 C/LiFePO4 and

other LiMPO4

C/LiFePO4 andother LiMPO4

Li4Ti5O12/NMC

C/LMO

C/LiFePO4& LiMPO4

HEV, EV, ESS power

in blends

Too expensive except space & aviation

Higher energyexpected

Tools, ESS high power

Almost everywhere

Various except high energy

11

Choice of positive active materials according to parameters

LiCoO2 NCA NMC LiMn2O4 LiFePO4

Energy Good Good Good Poor Average

Power Good Good Average/Good Good Good

Low T discharge Good Good Good Good Average

Calendar life Average Very Good Good Poor Average

Cycle life Average Excellent Good Average Good

Safety To ensure at batterylevel

To ensure at batterylevel

To ensure at battery level Average The most stable material

Cost High High High Average Average

Maturity High High Average High Average

. All are used in large batteries (alone or in blends) except LiCoO2 for cost reasons

. High voltage phosphates and spinels not yet taken in account (not enough mature)

1. Maturity and supply of materials

Qualification of industrial products is long and you must be sureof the content of your product: it can be long to be allowed tochange materials inside afterwards (years)

Obsolescence and availability of components need to beconsidered ; health and durability of suppliers is a concern

Customers wish to have two suppliers, or at least one supplierwith two plants in different places

This is a reason why the future generations of materials – not yetscaled-up or stabilized - are not yet taken in consideration

Same for silicon negative

17

2. Cell components

Electrode manufacturing is today similar to the portable cells,with a common hope of development of aqueous process(organic solvent free) for all (or almost all) positive chemistries

There were/are specific developments to stabilize the zone ofseparation between electrodes and avoid consequences of short-circuits:

> Shut-down effect

> Mineral heat resistance layer (e.g. alumina) at the surface of oneelectrode or separator to avoid direct contact of electrodes

Cans for large cells have also pressure sensitive systems to allowsoft opening different from the simple circuit breaker of smallcells in overcharge situation

18

2. Choice of cells

The proportion of prismatic cells (hard can or pouch) for portablecommunications increases:

> Better compactness and volume use in favor of energy increase

> Acceptance of limited life

The case is more complex for industrial applications:

> Same better compactness of prismatic assembly but:

> Cylindrical cells have often longer life

> Heat evacuation is compulsory to ensure long life especially forpower batteries

> Compactness with efficient thermal management is challenging orheavy for prismatic

Largest cells reach around 100 Ah; heat evaliation is important19

20

3. Battery System design

application

charge / power supply

communication

Battery with electronics

Module

Cell

interface

21IBG/SDU/H

L/

Mechanical Subsystem Prototype manufacturing

Electronics Software

Electrical Subsystem Thermal Subsystem

3. Battery system design

23

Process for optimal integration of battery systems

Various algorithms are developed according to customerdemands:

> E.g.: Battery modeling provides power prediction

0

50

100

-20

0

20

40

600

1

2

3

4

5

6

SOC (%)

Bat VL6P Power Prediction in discharge 10s

Temperature (°C)

Po

wer

(kW

)

24

Need of a signal for state-of-charge management

• If positive material is lithiated oxide, SOC algorithms are based on voltagevariation with SOC and integration of temperature and ageing factors

• Tricks are needed for phosphates where neither voltage nor resistance canbe used

Specific capacity of materials (mAh/g)

4

Ageing models

25

Number of cycles vs depth of discharge (dod) at 25°C

Scale: linear in x and log in y

10 kcycles and6 000 times

capacity

100 kcycles and20 000 times

capacity

26

4 Specialty applications

The first industrial application of Li-ion: batteries for satellites

Before the existence of Lithium-ion, geosynchronous satellitesused Ni-H2

Li-ion has a huge interest:

> Less weight for the same energymore payload

> Better efficiency less solar panels to charge the battery lessweight

Specific duties of geosynchronous or low earth orbit applications:

> 15 years calendar life, 90 cycles per year (GEO)

> 5 year life but heavy duty for LEO

> Withstand vibrations (launching) and radiation in space

Solutions to fulfill life specs: depth of discharge adjustment

> Challenge: increase dodmore energy or smaller battery

> And also increase specific energy

27

The first industrial application of Li-ion: satellite batteries

Battery for geosynchronoussatellite

28

Saft battery for driller: Hubblerepair

. Battery energy: < 10 kWh

. Life 15 years

. Used 2 eclipse periods per year

. Charged by solar pannels

. Should be to survive in space

. Expensive management withone bypass per cell. No safety issue after launching

. For low earth orbit:

. Life 5 years

. Several cycles per day

. Higher power needed

.more difficult duty

29

Li-ion for aviation batteries

28 V battery allowing weight saving versus present Ni-Cd batteries

More power available

NO MAINTENANCE

Direct integration of electronics and charger will also contribute to reduceweight and increase safety

First application Saft :

> Airbus A350XWB

Dreamliner problem could lead to delays

28 V Li-ion aviation battery

Li-IonBattery

30

4 Mobility applications

Li-ion battery for hybrid car

31

31

Mercedes – class S “S400 Blue hybrid”> Mild-Hybrid System: 19 kW boost / 32 cells

> In production since mid-2009

> Using Saft 6 Ah cyclindric cells

> Battery under the hood on passenger side

Pure EV Nissan Leaf

34

Battery technical characteristics:. Laminated Li-ion battery 24 kWhmade of 48 modules of 4 cells (2x2). Power > 90 kW. Energy density 140 Wh/kg. Autonomy 160 km. Life: 5 years ; e.o.l. at 80% initialcapacity. Under the floor and seats of thevehicle

car of theyear 2011

Charge:. duration < 8 hours on 220 V homeplug. fast charge: 80% capacity in 30min

Batteries built by AESC (jv Nissan-Nec)Sales began in April 2010

Next Renault car ZOECells from LG22kWh battery ; fast exchangeAir conditioning with heat pumpSales begin in March 2013

Bolloré Blue car: innovation in utilization

Innovation in utilization(Autolib)

Utilizes metallic lithium asnegative active material

35

Technical characteristics:. Energy 30 kWh. Power 60 kW. Specific energy 140 Wh/kg. Autonomy 250 km. Life: 10 years/ 1200 cycles. Operates at 60-100°C (Li polymer). LiFePO4 cathode

Available in Paris with a specificrenting system:. 2000 cars in operation ; 3000forecast. claim to be at breakeven in 2014

34

5 ESS applications

Grid limits

Grids are weak in certain areas:> Insufficient connection between zones:

• North/South Germany with excess of wind energy from the north

• In France Provence and Brittany refused high voltage cable or nuclear plantand are electrically isolated

• Grid power in insufficient in California

• Japan is an electrical and political island (no electrical exchange withneighbors) + Fukushima

The growth of intermittent energy is a factor of grid destabilization

> Voltage, frequency need permanent adjustment

Smart grids will have centralized or local wind or sun powerproducers

35

Energy storage for smart grids

36

ESS with Li-ion batteries

Our job at Saft is to propose answers to projects of energysupply associated with renewables:

> Residential storage (15 kWh)

> Power supply or peak shaving for isolated systems (1 MWsystems in 20 feet containers)

> High power batteries for network stability

Energy storage for telecom cabinets:

> 48 V outdoor batteries

Li-ion is well positioned when power is needed, typicallydischarges in 15 mn max (fast charge also needed)

International Management Meeting - March 27th, 28th, 29th 2012 - Jacksonville37

38

accu VL45E150 Wh/kg

Example of batteries for ESS applications

Energy supply

> 300 Wh

> 1U- 1/219 ’’

> 600 Wh

> 1U- 19 ’’

IntensiumFlexTension Maximum : 750V DCCourant Maximum: 300A, 300 sec

48 V2 300 Wh102 Wh/kg

3U- 19 ’’

40

6 Conclusions

Conclusion

Many industrial markets are still in infancy

> Aviation will survive to the Dreamliner incidents but needs time formaturation

> HEV, EV and other vehicles are emerging

> ESS for large systems and residential begins

For industrial manufacturers the challenge is to make moneywith Li-ion

> Competition is fierce

> Li-ion needs huge investments

> There is already cell production overcapacity

> Already two companies failed

c41

Thank you for your attention

42