Solvay’s New Developments in Electrolyte

Additives and Solef® PVDF Binders

Thomas Mathivet & Thierry Baert

AABC Conference January 30th – February 2nd 2017 Mainz, Germany

Agenda

1. Solvay in brief

2. Solvay Materials for Lithium ion batteries

3. SA 27 : New additive for Li-Ion electrolytes

4. Polymers for LIB combining high electrochemical

stability and ultra-high adhesion

5. Solid Polymer Electrolytes

6. Conclusions

2

3

Agenda

1. Solvay in brief

2. Solvay Materials for Lithium ion batteries

3. SA 27 : New additive for Li-Ion electrolytes

4. Polymers for LIB combining high electrochemical

stability and ultra-high adhesion

5. Solid Polymer Electrolytes

6. Conclusions

4

Industry Battery Roadmap met by Solvay LIB materials

5

R&I Labs Investment dedicated to LIB Market

We are able to support customers globally and locallyMarket needs quickly transferred to R&I and Innovative product and solution introduced to market

Partnership with leading institutes: EWHA (Korea), DoE in USA, FP7 H2020 in Europe, and CEA in France.

Dry Room

Experiment Room

6

Solvay in the Li-ion Battery Value Chain

Secondary

Battery

Cell

Manufacturing

Components

Electrolyte salts

LiTFSI, LiTA

ElectrolyteElectrolyte additives

F1EC / F2EC / TAB / SA

derivatives

Consumer Electronics

Computer

Communication

Energy & Construction

Transportation

Cathode

Anode

Separator

PVDF based binder

PVDF based binder

PVDF based coating

Specialty

polymers

Anode Active Material

Cathode Active Material

Solvent

Battery Cell

Cathode

Anode

Battery Pack

SOLVAY product Non SOLVAY Product

PE / PP Polyolefin

7

Agenda

1. Solvay in brief

2. Solvay Materials for Lithium ion batteries

3. SA 27 : New additive for Li-Ion electrolytes

4. Polymers for LIB combining high electrochemical

stability and ultra-high adhesion

5. Solid Polymer Electrolytes

6. Conclusions

8

Chemical Name SA27

Molecular weight 146.1

Melting point <-70°C

Boiling point 167°C

Viscosity(mpas) 2.5

Chemical property

F1EC VC SA27

Oxidation 6.4 5.1 6.7

Reduction 1.15 0.76 0.87

Electrochemical property

SA 27 is a new fluoro additive of Solvay for HV Li-ion

• SA27 is a liquid, low molecular weight fluorinated additive with a

comparatively broad electrochemical stability window.

9

Performance in cycling of SA27 additive

0 100 200 300 400 500 600 700 8000

20

40

60

80

100 No additive

VC 1.5 / PS 0.5

VC 1.5 / PS 0.5 / SA027 0.25

VC 1.5 / PS 0.5 / SA027 0.5

VC 1.5 / PS 0.5 / SA027 1.0

Cap

acit

y r

ete

nti

on

/ %

Cycle number

Cell NMC622/Graphite

Cell type : Pouch cell (stack type)

Standard : 1M LiPF6 in EC/EMC(3/7 v/v)

1C-chg./2C-dischg. 4.35-3.0V ; T=23°C

• At 1% concentration, SA27 increases by 15% the cycling efficiency (at 80% initial capacity)

• SA27 enables to improve the battery lifetime

+ 15%

VC= vinylene carbonate

PS=1,3 propane sultone

NMC622

10

SA27 in the high temperature (60, 80°C)

storage test

Without

SA 27

With 1,0%

SA 27

Cell NMC 622 / Graphite

Cells after storage test at 60ºC for 4 weeks &

80ºC for 1week

Standard : 1M LiPF6 in EC/EMC(3/7 v/v)

Additive : VC 1,5% ; PS 0,5%

VC= vinylene carbonate

PS=1,3 propane sultone

Anode surface protection

improvement

(post mortem analysis)

NMC622

11

• SA27 improves the stability of cells at high temperature

• Limited electrode degradation

• Safety improvement

100 200 300 400 500

900

820

700

Cap

acity

(mA

h)

Cycles

SA027 0.5% + VC 0.5%

SA027 0.5% + VC 1%

SA027 1% + PS 1%

VC 1%

SA027 0.5%

STD

`

`

`

`

Cell : LCO/NCA, Graphite

Cell type : Stacking pouch cell

Standard electrolyte : Standard : 1.15M LiPF6 EC/EMC/DMC 2/4/4

Testing temperature : Room temperature

LCO/NCASA 27 cycling performance with high nickel

system

80% of initial

capacityVC= vinylene carbonate

VC + SA27

• A synergy between SA 27 & VC enhances the cycling performance of the cell.

12

LCO/NCASA27 performance with high nickel system

+ 5.2 %

Re

co

ve

ry c

ap

acity(m

Ah)

- 6.2 %

Swelling Recovered capacity

VC= vinylene carbonate

Storage test : 70 °C, 1 week

Cell: LCO/NCA, Graphite

Cell typeStacking pouch cell

Standard electrolyte :

1.15M LiPF6 EC/EMC/DMC 2/4/4

13

Before storage

After storage

• Swelling and recovered capacity are significantly improved in presence of SA27

Agenda

1. Solvay in brief

2. Solvay Materials for Lithium ion batteries

3. SA 27 : New additive for Li-Ion electrolytes

4. Polymers for LIB combining high electrochemical

stability and ultra-high adhesion

5. Solid Polymer Electrolytes

6. Conclusions

14

15

Solef® PVDF for Electrode BinderCombining electrochemical stability of up to 4,5V with developments towards much

lower binder concentration

• From Standard PVDF to Solef® 5130 and beyond

Gen 1

Solef® 6010,

PVDF homopolymer

Molecular Weight

Increasing

Gen 2

Solef® 6020,

PVDF High MW

Chemical

Modification

Gen 3

Solef® 5130

modified PVDF• High Adhesion for

Large format LIBs

Multiple

Technologies

Beyond

Solef® 5120

Solef® 5140 (Exp)

modified PVDF

From Gen 1 to Gen 4: the 3% binder reduction brings a value of 10 Eur/kWh with a cost of only 2€/kWh

16

Ultra-High Adhesion Solef® PVDF Binder Grade:

Solef® 5140, a Step Further in Electrode Reliability

Solef® 5120 further addresses the improved dissolution and lower slurry viscosity

0

10

20

30

40

Solef 5130 Solef Ultra Adhesion

Peelin

g S

tren

gth

(N

/m)

TSC 65%

TSC 70%

®

Solef® 5130

Solef 5140®

Formulation [ %wt ]

PVDF Super C65 LCO

2 2 96

1 2 97

0,5 2 97,5

Formulation [ %wt ]

Solef® 5130 Super C65 LCO

1 2 97

• Slurry TSC 70%

• Electrode porosity 30%

• Thickness 70-80 µm

• Electrode porosity 30%

• Thickness 70-80 µm

® Solef 5130®

17

Transfer of, Proven Successful Technology to a New

PVDF Latex Generation

Solef® PVDF XPH latexes (experimental)• Solid latex content: 25% w

• pH: 3 (stable to pH adjustment to up to 13)

Crystallinity Calendering T Flexibility

Solef® XPH 838 Latex High 130°C Standard

Solef® XPH 859 Latex None < 60°C Excellent

Solef® XPH 884 Latex Medium 110-120°C Very good

New Solef® XPH Latex High 120°C Good

2. Particles packing & deformation

aggregation of PVDF primary particles & water evaporation

1. Aqueous slurry

dispersion of AM/Binder

3. Coalescence

Melting into Mechanically coherent dry film

18

A Range of Solef® PVDF Latex to Fit Adhesion and

Coating Process Requirements

• Solef® PVDF Latex for cost-efficient water-based processing

• Different grades designed for different processing temperatures

• Select the suitable grade, whether for ceramic binder or lamination promoter

* Not applicable

Me

ltin

gP

oin

t/°C

*

19

A Range of Solef® PVDF Latex to Fit Adhesion and

Coating Process Requirements

• Coatings with or without ceramic are proven to be feasible

PVDF Coating

Separator

Ad

he

sio

nN

/m

Formulation:

• 10% PVDF

• 90% Al2O3

PVDF Binders

Ceramic

Separator

Ad

he

sio

nN

/m

Agenda

1. Solvay in brief

2. Solvay Materials for Lithium ion batteries

3. SA 27 : New additive for Li-Ion electrolytes

4. Polymers for LIB combining high electrochemical

stability and ultra-high adhesion

5. Solid Polymer Electrolytes

6. Conclusions

20

Solid Polymer Electrolyte: a New, Safer and Durable Solution

Key Features

On-going Developments

High energy density architecture

Use of metallic Li anode and high voltage cathodes

Processabilityby conventional printing techniques

Flexibility

Safety

> No liquid electrolyte leakage

> No flammable ingredients

High ionic conductivity even at room T (1 mS/cm)

Ionic conductivity at low temperature

Electrodes/electrolyte interface management, new electrode structure design

Scale-up of the process

-6.00

-5.50

-5.00

-4.50

-4.00

-3.50

-3.00

-2.50

-2.00

-1.50

2.50 3.00 3.50 4.00

Liquid Electrolyte

PEO+LiTFSi

Electrolyte

New Technology:

PVDF-based+

mineral particles

While requiring improvements to fulfill all the battery challenges

21

1/T

F1EC,

F2EC, TAB

Additives for

electrolyte

Solef® PVDF

Binder

Solef® PVDF

Coating

LiTFSI

Main salt or

additive for

electrolyte

Solef® PVDF

Binder

TOWARDS SOLID-

STATE BATTERY:

Separator substitution

by gel/solid electrolyte

POLYMER

ELECTROLYTECATHODEANODE

Agenda

1. Solvay in brief

2. Solvay Materials for Lithium ion batteries

3. SA 27 : New additive for Li-Ion electrolytes

4. Polymers for LIB combining high electrochemical

stability and ultra-high adhesion

5. Solid Polymer Electrolytes

6. Conclusions

22

Conclusions

The development of new materials for Li-ion battery by Solvay are

oriented towards :

• Capacity and cyclability improvement

• New additives, solvents ans salts for Li ion electrolyte development

• Increased adhesion Solef® PVDF binders.

• Waterborn Solef PVDF Latex for Separator coating.

• Safety enhancement and production costs

• Polymer electrolyte solution.

23

We will be pleased to cover additional topics as materials as metal

replacement, for lighter battery pack housing, or flexible binders for highly

loaded electrodes, at our booth or at the poster session