lithium sulfur battery research progress in helis project · stripping and deposition tests 17...
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Lithium sulfur battery research progress in HELIS project
Robert Dominko
National institute of chemistry, Ljubljana, Slovenia
University of Ljubljana, Slovenia
Alistore-ERI, Amiens, France
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
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
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
• 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
5Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
- 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
6Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
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
7Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
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)
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
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
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
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
10Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
Al2O3 8.5nm Al2O3 21 nm
Al2O3 43 nm Al2O3 85nm
SEM pictures of Al2O3 coatings
11Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
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
layer Cel.2320+ 43nm 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
layer Cel.2320+ 21nm Al2O3 coating
layer Cel.2320+ 43nm Al2O3 coating
Cycle NoC
ou
lom
bic
eff
icie
ncy %
15 L/mgS, 2.8mgS/cm2, 1M LiTFSI TEGDME:DOL electrolyte, C/10
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
U – CELL EXPERIMENT: OCV test
Diffusion vs. migration
13
Celgard 232043nm Al2O3 coating
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
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
14Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
Post mortem analysis
15Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
F-rGO @ Li metal
16
J. Bobnar, M. Lozinsek, G. Kapun, R. Dedryvere, C. Njel, B. Genorio, R.Dominko, Sci. Rep. 2018
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
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
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
Morphology
18
SEM images of lithium electrodes after 100 cycles a) non-protected lithium foil, b) lithium foil with FGI.
J. Bobnar, M. Lozinsek, G. Kapun, R. Dedryvere, C. Njel, B. Genorio, R.Dominko, Sci. Rep 2018
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
19
SEM-FIB
Morphology inside the cracs.
J. Bobnar, M. Lozinsek, G. Kapun, R. Dedryvere, C. Njel, B. Genorio, R.Dominko, Sci. Rep 2018
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
Silylated cellulose coatings on lithium
20Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
Silylated cellulose coatings on lithium
21
Symmetric cells
current density of 0.5 mA cm-2
and 5 µLcm-2
1M LiTFSI TEGDME:DOLelectrolyte
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
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
22Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice
Acknowledgements
23
This project receives founding from the European Union‘s Horizont 2020
research and innovation programme under grant agreement No. 666221
Beyond Li-ion workshop Robert Dominko 2nd October 2018, Nice