Open Innovation responsible SOLVAY Aroma · PDF file08/10/2014 · STATE OF THE ART ELIBAMA STAKEHOLDERS CONFERENCE Newcastle, Oct 14. 2014 Reference : LiPF6 Since the pioneering Sony

TOWARD LITFSI ECO-EFFICIENT MANUFACTURING AND

RECYCLING PROCESSES

ELIBAMA STAKEHOLDERS CONFERENCE

Newcastle, Oct 14. 2014

François METZ Open Innovation responsible

SOLVAY Aroma Performance

STATE OF THE ART



Reference : LiPF6 Since the pioneering Sony Li-ion cell (early’s 90), still

almost exclusively implemented in modern LiB

Competitor Li salts : LiClO4, LiAsF6, LiBF4, LiB(C6H5)4, LiCl, LiBr,

Li(O3SCH3) and LiOTf

Maybe the most promising :

LiTFSI (CF3SO2)2NLi

M. Armand, (1985, 1990)

OBJECTIVES



TO PROMOTE THE USE OF LiTFSI

• Comparative physic, chemical and cycling

properties,

• Reducing LiTFSI FMC :

• Optimising the manufacturing process,

• Setting-up a recycling procedure

STATE OF THE ART



Physic and chemical

properties

→ standoff

LiPF6 LiTFSI

MW 152 287

% Li 4,7 2,42

g Li per mol 7,14 6,95

mp °C 195,5 235,8

decomposition

°C

(TGA)

107 > 330

H Yang, G. V. Zhuang, P. N. Ross Jr,

Journal of Power Sources 161 (2006) 573–579

Solvay internal results

Electrochemical

properties

→ standoff



Viscosity

→ advantage LiTFSI

Water resistance

Operating conditions :

1% w/w H2O, 40°C, 60h




Battery lifetime


Battery second life





SUMMARY



Compared to LiPF6, LiTFSI displays

interesting properties : • Thermic stability

• Water resistance

• Viscosity

• Battery second life

• Battery lifetime

• Cell capacity after storage

as additive

To reduce it, 2 directions were proposed to Elibama : • LiTFSI manufacturing process : Optimisation of the chemical key

step (CF3CO2K sulfination)

• LiTFSI recycling : set-up of a scalable process

However, LiTFSI main drawback is its FMC

(Full Manufacturing Cost).

STATE OF THE

ART



SOLVAY

Competitor

s

: key steps

KEY STEP

CHARACTERISTICS



Key step : TFAK sulfination

yiel

d %

conversion %

TFAK sulfination

An apparently simple reaction…

but with severe constraints…

• TFAK conversion has to be limited

to minimise TFSK degradation

• Remaining TFAK has to be

separated and recycled

1

1

11

• Identify reaction by-products

• Understand their formation pathways

• Evaluate their kinetics

• Establish a kinetic model

Identified and/or

quantified products





Real time measurements :

[TFAK], [TFSK] : Raman in liquid phase

[CO2], [SO2], [CF3H],… : μGC in gas phase

Results assessed by 19F NMR

condensor

Gas meter

CST + Rushton

μGC

Raman

T °C

• Mastering CO2 and SO2 concentrations, both in liquid and gas

phases : in situ, on line analyses



7550

90

70

Conversion rate

Se

lecti

vit

y

Sulfination @ P atmo : performance curve

Current process

Targeted performance

Experimental Curve

ELIBAMA WP2

Progress linked to

X + 10

x



Proof of concept established with a synthetic electrolyte

LiTFSI 65,4g 0,1mol

EC 114ml Homogeneous

DMC 114ml medium

CH2Cl2 225ml

water 450ml AL : LiTFSI 0,095mol 96%

OL : LiTFSI 0,0044mol 4%

dilution

LiTFSI recycling from synthetic electrolyte : 02GM059



Extension to a « real case » : CEA used pouched cells



Extension to a « real case » : CEA used pouched cells

• Separator PE/PP 110 x 3,5 cm

m = ~1,1g

• Cathode 38 x 3,3 cm

LiFePO4 (LFP) m = ~ 5,8 g

• Anode 46,5 x 3,2 cm

Graphite (G) m = ~ 4,5 g

17

17 ELIBAMA STAKEHOLDERS CONFERENCE


LiTFSI recycling :

Blocks diagramm 90% LiTFSI extraction

Further purification necessary



• Compared to LiPF6, LiTFSI displays interesting

physical, chemical and cycling properties ( 2

commercial flyers have been issued)

• The performances of its chemical process key step

has been significantly improvement (10%

selectivity gain → 7% FMC reduction)

• A scalable LiTFSI recovery process has been

developped,

• 2 patents have been issued (TFAK sulfination,

LiTFSI recycling)

But LiTFSI promotion still remains challenging



Industrial implementation of the

optimised TFSK process (« New TFSK »)

scheduled for 2015,

Further improvements under progress



The ELIBAMA project is granted by the European Commission under the

“Nanosciences, nanotechnologies, materials & new production technologies” (NMP) Theme

of the 7th Framework Programme for Research and Technological Development.

Documents

Open Innovation responsible SOLVAY Aroma · PDF file08/10/2014 · STATE OF THE ART ELIBAMA STAKEHOLDERS CONFERENCE Newcastle, Oct 14. 2014 Reference : LiPF6 Since the pioneering Sony