Lithium sulfur battery research progress in HELIS project · Stripping and deposition tests 17...

Lithium sulfur battery research progress in HELIS project

Robert Dominko

National institute of chemistry, Ljubljana, Slovenia

University of Ljubljana, Slovenia

Alistore-ERI, Amiens, France

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HELIS administrative information

14 partners from 7 countries – 2 large enterprises, 3 SMEs, 3 knowledge transfer institutions and 6 research laboratories.4 Alistore – ERI laboratories (http://alistore.eu/ )

Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice

http://alistore.eu/

HELIS administrative information

Type of action Project

budget

EU Funding Project

Start-End

CP – collaborative

project

€ 7.97 M € 7.97 M 1st June 2015

31st May 2019

EC Call NMP-17-2014: Post-lithium ion batteries for electric automotive

applications

Partners SAFT SAS, PSA, Solvionic, Picosun, Accurec, INERIS, CNRS, IREQ,

Chalmers University, Fraunhofer, Tel Aviv University, Munster University, Max

Planck, NIC

Target &

Deliverables

- Energy density, power, durability, ageing, safety, battery packs,

recycling, modeling, scale up of components from EUROLIS

Overall

ApproachM1,

Kick off

meeting

M2.

Prototypes

for ageing

study

M3.

Improved

prototypes

(separator)

M5.Improved

prototypes

(protected

lithium)

October 2018

June 2015October 2017

June 2016


• Nanostructured porous carbon host matrices

• Separator interlayers

• Electrolytes

• Lithium protection

Research directions in HELIS project

4Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice

Use of fluorinated ether TFEE 1,2-(1,1,2,2-tetrafluoroethoxy)ethane

- discharge capacity improvement and coulombic efficiency increase

- altered voltage profile

Electrolyte with decreased solubility of PS

S. Drvaric Talian, S. Jeschke, A. Vizintin, K. Pirnat, I. Arčon, G. Aquilanti, P. Johansson, R. Dominko, Chem. Mater., 2017, 29, 10037–10044


- 4 mg S/cm2 in the cathode

- 6.5 (10) µL/mg S of chosen TFEE electrolyte mixture- no LiNO3 additive- one layer celgard separator

Areal capacity equals close to 5 mAh/cm2.

High-energy Li–S cell

0 200 400 600 800 1000 1200 14001.5

2.0

2.5

3.0

10.0 L/mg S

U /

V v

s Li

/Li+

Specific capacity / mAh/gS

6.5 L/mg S

0 10 20 30 400

500

1000

1500

6.5 L/mgS capacity

10 L/mgS capacity

6.5 L/mgS efficiency

10 L/mgS efficiency

Dis

char

ge c

apac

ity /

mA

h/g S

cycle number

0.2

0.4

0.6

0.8

1.0

cou

lom

bic

effic

ienc

y

S. Drvaric Talian, S. Jeschke, A. Vizintin, K. Pirnat, I. Arčon, G. Aquilanti, P. Johansson, R. Dominko, Chem. Mater., 2017, 29, 10037–10044


Nanoporous carbon as hosting material

0 2 4 6 8 10 12 14 16 18 200

400

800

1200

1600

2000

Charge

Discharge

Spe

cific

cap

acity

/ m

Ah

g-1

Cycle number

carbonate based electrolyte

C/5 cycling rate

1mg S/cm2 loading (40 wt % S)

0 500 1000 1500 2000 25001.0

1.5

2.0

2.5

3.0

3.5

1st cycle

5th

cycle

10th

cycle

18th

cycle

U /

V v

s. L

i / L

i+

Specific capacity / mAh g-1

SampleBET Surface

AreaDFT Surface

AreaCumulative

Pore VolumeSubnanometer Pore Volume

Pore Diameter Mode

CDC sample type 1 1698.9 m2/g 1632.1 m2/g 0.751 cc/g 0.438 cc/g 0.666 nm


0,0 0,5 1,0 1,5 2,0

0

20

40

60

80

100

120

140

160

180

200

Li2S

x -

short chains

U /

V v

s Li

/ Li

+

Rel

. am

ount

of s

ulfu

r

com

poun

ds (%

)

x in LixS

Li2S

Sulphur

Li2S

x - long chains

0,0

0,5

1,0

1,5

2,0

2,5

3,0

2465 2470 2475 2480 2485 24900,0

0,5

1,0

1,5

2,0

long chain Li2S

x (39%)

Sulfur (61%)

Discharge at

y = 0.64 in LiyS

Nor

mal

ised

abs

orpt

ion

E / eV

Experiment

Fit a)

2465 2470 2475 2480 2485 24900,0

0,5

1,0

1,5

2,0

Li2S

x - short chain (51%)

Li2S (13%)

Li2S

x - long chain (36%)

Discharge at

y = 1.57 in LiyS

Nor

mal

ised

abs

orpt

ion

E / eV

Experiment

Fit

b)

Mechanism in carbonate solvents

R. Dominko, A. Vizintin, G. Aquilanti, L. Stievano, M.J. Helen, A. R. Munnangi, M. Fichtner, I. Arcon, J. Electrochem. Soc. 165 (1) A5014-A5019 (2018)

8

Simillar mechansim going trough PS formation

Difference in existance of long chain PS and short chain PS (Li2S2 like)


Ion selective separators

9

Commercial Li1+x+yAlxTi2-xSiyP3-yO12 membrane from OHARA

A. Vizintin, ...RD, ChemElectroChem, 2014, 1, 1040-1045

0 10 20 30 40 50 60 70 80 90 1000

200

400

600

800

1000

1200

1400

1600

Ceramic separator

F-rGO_3 interlayer

D

isc

ha

rge

ca

pa

cit

y /

mA

h g

-1

Cycle number

A. Vizintin, ...RD, Chem.Mater., 2016, 1, 1040-1045


Picosun - ALD-modification of Celgrad separators Different thickness of Al2O3 or ZnO ALD coatings on

Celgard 2320 separator Coatings on both sides Uniform deposition which depends on pretreatment of

Celgard separator Repeatable coatings Price few € / m2

Electrochemical tests at NIC

ALD modification of Celgard separator


Al2O3 8.5nm Al2O3 21 nm

Al2O3 43 nm Al2O3 85nm

SEM pictures of Al2O3 coatings


Electrochemical characterization

12

0 10 20 30 400

200

400

600

800

1000

1200

1400

cycle No.

2 layers Cel. 2320

layer Cel.2320+ 8.5nm Al2O3 coating

layer Cel.2320+ 21nm Al2O3 coating


Ca

pa

city /

mA

h/g

0 10 20 30 4090

95

100

105

110 2 layers Cel. 2320

layer Cel.2320+ 8.5nm Al2O3 coating



Cycle NoC

ou

lom

bic

eff

icie

ncy %

15 L/mgS, 2.8mgS/cm2, 1M LiTFSI TEGDME:DOL electrolyte, C/10


U – CELL EXPERIMENT: OCV test

Diffusion vs. migration

13

Celgard 232043nm Al2O3 coating


U – CELL EXPERIMENT: Investigation of polysulphide

diffusion under constant potencial (2 V) – Picosun 43 nmLi foil

GEN1 electrolyteNi foil

LiPS solution

in GEN1

Diffusion vs. migration


Post mortem analysis


F-rGO @ Li metal

16

J. Bobnar, M. Lozinsek, G. Kapun, R. Dedryvere, C. Njel, B. Genorio, R.Dominko, Sci. Rep. 2018


Stripping and deposition tests

17

Electrolyte excess Optimized amount of electrolyte (3.3L/cm2)

Stripping and depositions conditions:Symmetrical cell (Li-Li configuration)0.5 mA/cm2 for 2 hours

J. Bobnar, M. Lozinsek, G. Kapun, R. Dedryvere, C. Njel, B. Genorio, R.Dominko, Sci. Rep 2018


Morphology

18

SEM images of lithium electrodes after 100 cycles a) non-protected lithium foil, b) lithium foil with FGI.



19

SEM-FIB

Morphology inside the cracs.



Silylated cellulose coatings on lithium


Silylated cellulose coatings on lithium

21

Symmetric cells

current density of 0.5 mA cm-2

and 5 µLcm-2

1M LiTFSI TEGDME:DOLelectrolyte


Conclusions

Li-S batteries perspectives

- High sulphur ratio in the C/S composite with high electrode loading

- Low electrolyte quantity

- First we need to have fully protected lithium metal than we can optimize sulphur cathode and electrolyte amount


Acknowledgements

23

This project receives founding from the European Union‘s Horizont 2020

research and innovation programme under grant agreement No. 666221


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Lithium sulfur battery research progress in HELIS project · Stripping and deposition tests 17...

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