Innovation in Industrial Technologies: the case of batteries

Anne de GuibertAarhus 20 June 2012

Energy availability in a moving and clean world

Energy storage has a key role to play in our world societal evolution

> Each new generation of nomad communication devices (phone, computer, tablets…) needs batteries with increased energy density storage

> More electric vehicles (cars, boats, planes…) will be at least a partial solution to progressive oil scarcity as well as CO2 or particles reduction (societal demand). They require top-performing batteries with long life, low cost, high energy/power, good safety

> Weak networks and integration of intermittent renewable energy on the grid beyond 20-25 % will need energy storage. Here also batteries will play their part, especially for high power demands or small/mid size residential systems

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The various storage possibilities: energy and power

100 MW

10 MW

1 MW

100 kW

10 kW

1 kW

0.1 kW

0,001 0,01 0,1 1 10 100 1000 10 100 1000kWh MWh

Hydro and large compressed air

Energy batteries

Redox-flow and reversible fuel cells

SMES

Flywheels

Compressed air

Supercapacitors

Power batteries

Batteries for portable applications

1 week storage Seasonal storage

EC Document “Energy Storage : A key technology for decentralized power, power quality and clean transport” - 2001

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Saft. A world leader in high technology batteries

Saft is recognised worldwide as the leading designer, developer and manufacturer ofnickel-based battery solutions for the industrial, transport and professional electronic sectors.

The Group is the world’s leading designer, developer and manufacturer of high-performance primary lithium and rechargeable lithium-ion(Li-ion) battery systems for both civil and military markets.

World leader in lithium-ion satellite batteries, Saft is also delivering its Li-ion technology to new applications in clean vehicles and energy storage systems.

The Saft Group in 2011

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Content

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Present choices and deployment status

The 3 steps of improvement roadmap 2014-2020

Towards industrial cells at 250 Wh/kg ?

Beyond Li-ion : Li-sulfur, Li-air, sodium or magnesium batteries ??

Materials: the heart of batteries

Batteries for more electric, cleaner vehicles

Batteries are designed for four levels of applications and specifications:

> Stop-and-start : lead-acid batteries, improved from starter batteries + possibly supercapacitors , Li-ion. Usable energy <500 Wh

> Hybrids with the emblematic Toyota Prius (NiMH batteries). More recent hybrid cars use Li-ion technology. Available energy < 1.5 kWh : small battery, high power

> Plug-in : 5-10 kWh> Pure electric : 20 kWh minimum, 30 or more preferred.

Lithium technology

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PROPRIETE SAFT 7

Lithium-ion hybrid vehicles application

From120V to 400 V ; 1-2 kWhNCA cathode material for the best power and life

in application since 2009 in Germany and USAMercedes S400 Hybrid with Saft Li-ion

Pure EV Nissan Leaf

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Battery technical characteristics:. Laminated Li-ion battery 24 kWh made 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% initial capacity. Under the floor and seats of the vehicle

car of the year 2011

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

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

Bolloré Blue car

Innovation in utilization (Autolib)Use metallic lithium as negative electrode active material (alone against all other manufacturers)

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Technical characteristics given by the manufacturer:. 30 kWh battery. Power 60 kW. Specific energy 140 Wh/kg. Autonomy 250 km. Life: 10 years/ 1200 cycles. Operation at 60-100°C ( Li-polymer technology)

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NiMH: a powerful battery for heavy duty

Saft Ni-MH 750 V 30 kWh 200 kW battery: system mass: 1 t for tram

Alkaline battery with metallic rare earth alloy as negative active material

open battery systemopen battery system

cell/module

Batteries for stationary applications

Up to now, 90 % of batteries for storage application utilized lead-acid technology. The 10 % remaining are NiCd used for severe conditions applications

New applications (smart grids, association with renewable energies) are lithium-ion oriented: long life, absence of maintenance, high power for frequency control are determining qualities

High specific energy is not as important as for mobility. Life and cost are key issues, power can be.

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accu VL45E150 Wh/kg

Li-Ion for standby energy delivery

Energy systems

> 300 Wh> 1U- 1/2

19 ’’

> 600 Wh> 1U- 19 ’’

IntensiumFlex Tension Maximum : 750V DCCourant Maximum: 300A, 300 sec

48 V2 300 Wh102 Wh/kg

3U- 19 ’’

Evolion, the last born standby energy storage module

Module of 14 cells – 80 Ah

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. Modular complete systems with charger and electronics in standard containers

. Energy up to several MWh

CONFIDENTIEL SAFT 14

From very high power to very high energy

C/100

C/10

C

10C

100C

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100

1 000

10 000

100 000

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Energy [Wh/kg]

Po

wer

[W

/kg

] 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)

Specific energy at cell scale

Standard Lead-Acid

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Versatility of Li-ion subsystems: innovation in materials is essential

Li-ion chemistries

C/NCAC/LiCoO2

C/NMC(s)

new generations for >0

& <0C/LiFePO4 and other LiMPO4

C/LiFePO4 and other LiMPO4

Li4Ti5O12/NMC

C/LMO

C/LiFePO4

& LiMPO4

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The great majority of emerging applications use Li-ion batteries: strengths & weaknesses of the technology

Strengths :> The best specific energy (up

to 230 Wh/kg in energy cell for consumer application)

> Good volumetric energy> Excellent cyclability> Good calendar life> Very high power possible (up

to 12 kW/kg in pulses)> Excellent energetic efficiency> Numerous subsystems:

possible optimization for different specifications

Weaknesses :> Global cost of technology> Complex electronic

management compulsory> Safety of large cells and

batteries in abusive conditions needs further improvement

> High power chargeability to improve, especially at low temperature (ability to charge and discharge at the same rate)

Expressed needs: guidelines for the roadmap

Higher specific energy and energy density for pure EVs and plug-in Specific power increase for hybrid vehicles without life decrease; ability to charge and discharge at the same high rate (HEV & standby frequency regulation) Reliability & safety level EUCAR IV minimumLife 8 years for cars (end of life -20% capacity), more for stationaryCost decrease for all applications

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Bases of roadmap for batteries improvement

At short/mid term, to take the best from Li-ion recent technical solutions for incremental improvements:

> To increase energy or specific power available > To optimize choices for applications (global demands often contradictory)> To simplify/standardize systems for cost reduction while keeping the same

safety level

In parallel, to study the feasibility for industrial large batteries or solutions emerging soon in portable cells (ex. Si et composites Si-C) or for known materials in development (‘NMC Li rich’)

Increase networking with Universities on breakthrough innovations for the following generations and the ‘after Li-ion’

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Step 1: implementation 2-3 years ahead

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Example: draw more from positive active materials (EV)

Except for LiFePO4 where nothing more can be expected, charge of cells is voltage limited (NMC, NCA, LCO) though the material is not fully charged:

> To get a sufficient calendar life by limiting electrolyte decomposition and avoid structural changes at the surface of materials

> To Improve safety> To use less materials

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NCA, NMC additional capacity at high voltage

LiFePO4 : no additional capacity

Possibility to recover 10-15 % more capacity

Example: draw more from positive active materials (VE)

To increase available energy, the solution of voltage increase has begun to be implemented in portable cells with limited life. Industrial applications need much longer life and safe big batteries which are developed :

> Using surface protection (nano coatings) for interface stabilization> Safety being reinforced by other methods (HRL)> With necessary research on electrolytes and additives

Optimization for applications can be done by different choices of materials and their mixes to combine positive effects and decrease drawbacks:

> trade-off to find for power/cost/life safety

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Results expected within the next 2-3 years

Improvement given in example plus others should allow a 20% of specific energy (keeping the same life)Price decrease per kWh will come from better use of materials, process, scale-upWhat we can do for battery management simplification and better knowledge of the ageing behaviour will also contribute to cost decrease

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Thinking 3-6 years ahead

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Second step: Roadmap towards 250 Wh/kg

Availability of new materials is the key issue:> Nature of materials & type of reaction determine theoretical capacity> Organization (size, nanos or not, conductive additives, coating, blends,,

no critical raw source…) helps to go towards theoretical capacity

The gain on one polarity becomes marginal when one polarity has a capacity 4-5 time higher than the other one: both capacities should be increased in an equivalent manner for the best efficiency

The most advanced materials to progress towards the target> Negative materials based on Si & Sn> NMC lithium rich for positive active materials

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TODAY

“LiNiO2”

Sn

How can we continue to increase specific energy ? P

ote

nti

al

vs

Li/

Li+

(V

)

Capacity (Ah/kg)0 200 400 600 800 1000 1200 3800 4000

Neg

ati

ve

mat

eria

lsP

osi

tiv

e m

ater

ials

Li metalGraphite

Other carbons Si-compositesd = 2.3

Intermetallicsd = 4- 8

3D metal oxides

Nitridesd = 2.1

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3

4

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2

1

Sn-C

Phosphides (d 8)

“5V”

“LiCoO2”LiMn2O4&LiMnPO4&LiNMCs

“MnO2”

Vanadium oxides(V2O5, LiV3O8)

Polyanionic compounds(Li1-xVOPO4, LixFePO4)

5.0V

4.2V

4.7V

4.9V

“LiMnPO4” (170 mAh/g)

“Doped LiMn2O4” (100-135 mAh/g)

“LiCoPO4” (160mAh/g)

Li4Ti5O12

Si

TOMORROW

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Challenge: find a mean to contain LixMy volume changes on charge / discharge and to improve consecutive capacity loss on cycling :

Nano-sized particles & Electrode structuration ; Limit the insertion in the case of Si : Li1.7Si (1600 mAh/g).

Between all Li-metal alloys, Li-Si and Li-Sn are the more interesting …

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In C Bi Zn Te Pb Sb Ga Sn Al As Ge Si

Ca

pa

cit

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mA

h/g

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Li1.7Si Li2.3Si Li3.2Si Li4.4Si : 4200 mAh/gVolume changes :

120% for Li1.7Si

160% for Li2.3Si

240% for Li3.2Si

320% for Li4.4SiLi4.4Si, 1000 mAh/g,

volume change : 280%

Volumes changes of

carbon around 12 %

New negatives: solving the poor cycle life issue

Si or Sn swell during lithium insertion (charge) Consequence is materials desagregation, conductivity loss, and need to

reform passivation layer at each cycle Research programs everywhere in the world propose possible solutions

CHARGE DISCHARGE

Solutions envisaged

Only partial use of materials capacity (less swelling)Nano structures to contain siliconAdditives for stabilisation

Matsushita announces the first 18650 cell at 3.6 Ah with silicon negative (end 2012)Life should not be more than 200-300 cyclesStill very insufficient for cycling industrial applications, but substantial No safety data

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On the positive side: what’s new ?

New high capacity and high voltage NMC:> Overlithiated materials> Containing two different phases: Li2MnO3 and Li(NixMnyCozO2)

Must be charged at 4,6 V vs Li minimum for activation > Critical point today in terms of electrolyte

Objective: 230 mAh/g (+25%). Not ready industrially

Other families of polyanionic compounds could also be interesting if voltage is sufficient: sulfates, borates…

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Beyond Li-ion

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Beyond lithium-ion

Lithium-sulfur: 300 Wh/kg ?

Advantages> Sulfur is los cost and abundant> High capacity ( exchange 2

electrons)

Limitations and problems> Voltage lower than 3 V> Insulating discharge materials

(rapid ageing)> High self-discharge of

intermediate discharge compounds in organic media

> Risk H2S

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Numerous projects running> Polyplus + Sion Power, Oxis Energy : industrial projects> Nanostructured electrodes sulfur/mesoporous carbon(Univ.München)> Task Force of European network Alistore> Research step not finished

Conclusion

Batteries are key enabling technologies and are on the critical path of many innovations

Materials are the core of battery

A substantial part of the results on materials has been obtained in the frame of cooperation between materials manufacturers / battery manufacturers, and support of European Commission in many cases

As everybody, we have our valley of death: long duration of qualification, cost of demonstrators

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Thank you for your attention

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