AMELIE : Advanced Fluorinated Materials for High Safety, Energy and Calendar Life

Li Ion Batteries

European Green Car Initiative 3d European Green Car Initiative – Project clustering Event

July 11 & 12 2012Th BAERT

Outline

AMELIE’s new Materials in Li ion Battery.

• Motivation, objectives, key Milestones

• Key progresses at Mid terms

• The electrodes.

• The interaction new Electrolyte / new Separator

• Eco-design, Recycling and LCA.

• Partial Conclusions

Project general information

Project full title: Advanced Fluorinated Materials for High Safety,

Energy and Calendar Life Li Ion Batteries.

Coordinator contacts: Thierry.Baert@Solvay .com

Starting Date: 01 Jan 2011

Ending Date: 01 Jan 2014

Budget Total/Funding: 5,2 MEUR / 3,5 MEUR

Partners:

Motivation and objectives.

� Focus on an increased autonomy of EV/PHEV with improved safety of the

battery and cost controlled improved by recycling of some higher value

materials.

� Research needs towards develop of a higher specific energy cell with a

high voltage cathode material, and the corresponding stable electrolyte

(solvent and Salt) with new separators, binders and extended recycling

process

� Approach based on a new electrolytes will be based on fluorinated

solvents, Sulfonimide salts, specific additives to decrease the fading,

combined with fluorinated polymers as binders, and components of new

separator

Specifications of the final deliverable.

0

20

40

60

80

100

Energy

Power

Calendar Life

PriceCycle Life 80¨DoD

Operating Temperature

Recyclability/ Reuse

2010

Project Target

2015

>200 Wh/kg in a 12,5 Ah Primatic wounded soft package cell

650 W/kg, 50% SOC, 2C

Self discharge : < 5%/ month at 25 Cand < 10% at 45 C

80% Capacity remaining @ >1000 cycles

and within V limits at 25 C (100% DoD,1C, Vlimit)

+ 5 Safety test : mechanical, thermal (130 C), and 3 electrical.

Motivation / objectives / milestones

During the 1st Half of the project, mainly developments at lab scales are performed.

Testing of 2 to 4 Pilot 2 Ah iterations will be running during the 2d half.End of 2013 the final cell will be scale-up to 12,5Ah.

End 2012 the electrolyte and separator solution will be implemented in this cell.

At mid term (July 2012) the scale-up jobs (first up to 2,5 Ah cell) will be starting by the production of electrodes.

2011 2012 2013

• General Milestones plan.

Cells testing at Lab level

Key Progress in 2011

• The High Voltage cathode material has been selected as LNMO. The adequate volume for testing have been produced at CEA.

During the 1st Half of the project, mainly developments at lab scales are performed.

Testing of 2 to 4 Pilot iterations will be running during the 2d half.�End of 2013 the final cell will be scale-up to 12,5Ah.

2011 2012 2013

• Developments of new (PVDF based )polymers as binders and for separator

• The formulation of cathode and anode have been design including namely the binder selection. Some fine tuning will be done during the scale-up phase.

• Developments of new additives for the Cathode

Cells testing at Lab level

Key progress in 2012

During the 1st Half of the project, mainly developments at lab scales are performed.

Testing of 2 to 4 Pilot iterations will be running during the 2d half.�End of 2013 the final cell will be scale-up to 12,5Ah.

2011 2012 2013

• Prototype cells have been compared to our references cells (Commercial 18650 cell and own electrodes produced with commercial NMC ref material), testing the new electrodes.

• 5 different salts have been designed and produced. A preliminary screening of performances lead to select 2 of them that are under testing regarding their compatibility with the new solvents (going to binary mixtures), new additives, and the polymer selected for the separator.

• New polymers for separators tested with different reinforcement technologies.

Cells testing at Lab level

Main technical activities - on Electrodes

• The high Voltage cathode material (LNMO

4,9 V) has reached the scale-up phase.

A low content PVDF binder has been

selected.

• The Anode has been formulated with a

selection of Graphite, CB and with

different type of PVDF binders.

• The most adapted formulation has been

selected.

• The slurry properties have been studied

as well, to optimize the coating production

process.

Main technical activities - on Electrolyte/Separators

• The interaction new Electrolyte / new

PVDF Separator have been tested in

different configuration.

• Major improvements of the mechanicalproperties have been obtained and give

access to thinner membranes, lower

impedance.

• The production process at lab level still

remain challenging to tune and to control

avg pore size and their size distribution

repartition, especially when reinforced.

Main technical activities - on Separator

• Membranes have been cycled in cell with accepable results, but the thickness need to be reduced down to 20µm or lower.

1

10

100

1000

10000

-30 0 30 60 90 120 150 180

Storage

modulus

(MPa)

T (°C)

effect of NCC addition on dry

membranes

composite Solef

21216 + 1% whiskers

Solef 21216

composite Solef

21216 + 6% whiskers

composite Solef

21216 + 9% whiskers

composite Solef

21216 + 12%

whiskers

X 3

X 10

Main technical activities – Electrolyte/Separator

• The electrolyte formulation based on new fluorinated solvents, salts based on sulfonimide, varying from fully or partially fluorinated, alkyl or alkoxy.

• At a first step solvents were tested with LiTFSI as a simple Sulfonimide.

• We work on the corrosion issue of the Alu collector linked to these electrolytes types at high voltage.

• The interactions between the different polymers and these electrolyte components have been analysed. Better understanding of the interaction with special PVDF copolymers and fluorinated solvents has been generated.

Membranes

Polymer/ Electrolyte interactions : Wettability at filling, homogeneity, safety of gel and effect on power.

Electrolyte :

Salt / Solvents /

additives

FluorinatedSalts

Fluorinated Polymers

FluorinatedSolvents

Main technical activities – on half and full cells

• Full cells have been tested, with new cathode, new anode, and additives

• New dense and porous separators have been tested but thickness need to be reduced to decrease impedance and cost.

• First estimations has showed that with preliminary results the target of 200 Wh/kg would be achievable considering a cell voltage of 4,9V.

0 5 10 15 20 250

100

200

300

400

500

Ch

arg

e c

ap

ab

ilty

C/102C1CC/2C/3C/5

Amelie_SLALNMO_X23 T = 30°C

LNMO: 5.00 mg

SLA-1025: 1.62 mg

SLA-1025/LNMO: 0.82

Electrolyte: LF30 + 1.6% F1EC + 2% SA

Sp

ecific

ca

pa

city /

mA

h g

-1

SL

A-1

02

5

Cycle number

Charge Discharge

Discharge capability at 30 C

Life cycle analysis, end of life and recyclability

• Recycling

– Recycling at end of life aim to reach an overall target of 64%(gravimetric).

– All the newly designed AMELIE battery components of the batteries and the production routes are under evaluation in term of environmental impact.

– With a strong focus on the recycle rate target of EU Battery Directive EC/66/06 at the lowest possible cost.

• Eco-design.

– Eco-design follows the whole project process with recommendations for recycling/recovery/reuse.

– All routes using chemical way for recycling will be analysed against the requirements for REACH and ROHS.

– Besides the focus on electro active materials, the project will follow eco-design recommendations for electrolyte and membranes.

– The Eco-design will not be restricted to the recovery of inorganic materials (e.g. electrodes materials and current collectors), but a special attention will be paid to environmental friendly elaboration process, (including water based processes and extrusion of membranes)

Conclusion (Partial, for today..)

• Main achievement obtained on coin cells at Lab level.

– High voltage active materials giving access to 200 Wh/kg.

– Electrolyte improvement based on additives.

– First Separators at Lab level.

• Next steps.

– Scale up and optimize formulation.

– New selected salts and solvents for electrolyte under testing.

– Improve reliability of production of Separator at low thickness and the functionalization of the separator

• Major activities and deliverables in the coming year?– Pilot cells to be cycled according to the projects specifications.

– Performances of electrolyte/separator set.

• What are the risks and challenges?– Performances of electrolyte/separator set.

• Regarding cyclability

• Regarding Electrolyte (Al collector corrosion) and best fit with separator.

– Safety remains a question that cannot be solved on lab cells

• Extension of Topics that may need further collaborations.– Characterising ageing and the contribution of the separator/electrolyte set to leverage future

technologies as Solid electrolyte batteries, Li-S and LiAir.

Thank you for your kind attention