Evaluation of solid electrolytes
for all solid state Li-S batteries
X. Judez, H. Zhang, I. Aldalur, M. Piszcz, C. Li, L. Otaegui, J.
Zagórski, L. Buannic, A. Llordés,T. Rojo, J. Kilner, M. Armand,
Lide.M. Rodriguez-Martinez
2017
2017
©C
IC e
nerg
iGU
NE
. 2017 A
ll rights
reserv
ed
London 26th April 2017
Lide.M. Rodriguez-Martinez
Introduction11
Why solid?22
Results on solid Li-S batteries33
2
Results on solid Li-S batteries33
Conclusions & future work44
Acknowledgements55
Project launch &
Identification of
Research Areas’
Strategic lines.
Definition of operative
model and talent
recruitment
First industrial collaborations
I Symposium Nabatt
Na batteries re-development
ABAA 8
Launch of LiS activity
Launch of FAULTS
program
Recently created project. Beginning of the research activity in 2011
Introduction CIC = Centre for Cooperative Research in Energy Storage11
4545 6969
Electrochemical testing
lab completed
Organic lab completed
Physicochemical lab
operational
2014201320122008 - 2011 2015
recruitment
1st Edition of Congress
“Power our future – POF”
Na batteries re-development
2nd Edition POF
Launch of
Prototyping line’s 1st Phase
Electrochemical testing lab
1st phase
Highest reported
conductivity in garnet
electrolytes
2016
5th Anniversary and
Prototyping line’s
Inauguration
252522
4545
6060
6969
7777
8383
Launch of platform facilities
(XRD, EM, XPS, ssNMR)
Chemical lab operational
1st patent in Solid hybrid
electrolytes
3
Electric
traction
Electrical
networksSolar
thermal
power
Consumptio
n
CIC visioning… RVCTI (Basque Science, Technology and Innovation Network)
EnergiBasque 2.0
Strategic framework
Marine
Wind
Industrial
energy
efficiency
Renewable
Primary energy
Consumptio
n
4
Introduction11
Why solid?22
Results on solid Li-S batteries33
5
Results on solid Li-S batteries33
Conclusions & future work44
Acknowledgements55
Develop safe, cheap, sustainable and durable novel solid battery concepts
Polymer all solid batteries
Ceramic all solid batteries
� Safe
� Flexible membranes, cheap (upscalable
processing)
� Targets: 10-3 S/cm at 70ºC,
towards increased conductivity
mechanical strength
� Challenges: C-rate, stability, area specific
capacity, dendrite suppression
SAFETY
LIFECOST
22 SOLID BATTERIES
6
Ceramic all solid batteries
Composite concepts
� Safe
� HV stability
� Rigid membranes, complex processing
� Targets: 10-3 S/cm at RT,
dense thin film fabrication
� Challenges: stability, manufacturing
competitive routes,
compatibility, novel
configurations, interfaces,
COST
LIFE
POWERENERGY
DENSITY
COST
APPLICATION
SUSTAINABILITY – LIFE CYCLE
Li & Na metal batteries, HV solid batteries, Li-S solid batteries
400
600
800
1000
Gra
vim
etr
ic E
ne
rgy
De
ns
ity
(W
h /
kg
)
Polymer 10 um
Polymer 40 um
Polymer 100 um
400
600
800
1000
Gra
vim
etr
ic E
ne
rgy
De
ns
ity
(W
h /
kg
)
400
600
800
1000
Gra
vim
etr
ic E
ne
rgy
De
ns
ity
(W
h /
kg
)Ceramic 10 um
Ceramic 40 um
Threshold of electrolyte thickness
Cathode: 75%S / 20%C / 5% binder, S utilization = 1000 mAh / g
22 SOLID Li-S BATTERIES
0 2 4 6 8 10
0
200
400
Gra
vim
etr
ic E
ne
rgy
De
ns
ity
(W
h /
kg
)
Areal capacity (mAh / cm2
)
0 2 4 6 8 10
0
200
400
Gra
vim
etr
ic E
ne
rgy
De
ns
ity
(W
h /
kg
)
Areal capacity (mAh / cm2
)
Liquid E/S = 3
Liquid E/S = 5
Liquid E/S = 10
LIB (ceramic, Li)
0 2 4 6 8 10
0
200
400
Gra
vim
etr
ic E
ne
rgy
De
ns
ity
(W
h /
kg
)
Areal capacity (mAh / cm2
)
Ceramic 100 um
• Liquid Li-S: E/S < 3, there is no big potential for improvement
• Polymer Li-S: Fairly easy to achieve high energy density when separator thickness < 100 µm
• Ceramic Li-S: it is competitive only when the thickness of separator < 40 µm
7 Chunmei. Li et al., Journal of Power Sources, 326 (2016) 1-5.
Technology
Targets
� Safe, low cost, competitive high
energy density batteriesFirst phase (end 2018)
� Polymer rich systems
� > 2 mAh/cm2 ( 400Wh/kg)
� RT-70ºC
� stable 500 cycles
� S utilisation ≥ 1000 mAh / g
� S loading > 60%
Objective of our work22
Materials and
Processing
Technology
� Scaleable techniques
� Simple processing
� Low cost/reduce expensive materials
� Towards water based formulations
Second phase (end 2019)
� a) Ceramic rich systems
� b) Incorporation of novel RT
polymer conductors
8
Introduction11
Why solid?22
Results on solid Li-S batteries33
9
Results on solid Li-S batteries33
Conclusions & future work44
Acknowledgements55
Methodology and approach33
First phase (end 2018)
� Polymer rich systems based on PEO (SPE)
1) Choice of salt
2) Cathode development
3) Electrolyte development
1) PEO + LiFSI* or LiTFSI salts [EO:Li = 20:1]
2) Cathode development
“Simple cathodes”:
S: 30-50%wt
C (KJ600): 15%wt
SPE: balance
3) Electrolyte development
10
* H. Zhang, et al., Solid State Ionics 2014, 256, 61; H. Zhang, et al, Polymer 2014, 55, 3339; H. Zhang, et al., J. Fluorine
Chemistry 2015, 174, 49; H. Kim, et al., Adv. Energy Mater. 2015, DOI: 10.1002/aenm.201401792; Camacho-Forero et al.,
2017. J. Phys. Chem. C 121, 182–194. doi:10.1021/acs.jpcc.6b10774
Total ionic conductivity, Li transference number, 70ºC (this work):
PEO/LiFSI σT: 7.58 × 10–4 S/cm; T+= 0.12
PEO/LiTFSI σT : 7.08 × 10–4 S/cm T+= 0.15
3) Electrolyte development
Effect of salt
Composite electrolytes
Novel materials
Cyclic voltamperometry
LiTFSI/PEO, 70ºC, C/20 initial cycle
LiFSI/PEO, 70ºC, C/20 initial cycle, 40%S
Effect of salt (LiTFSI vs. LiFSI)33
Xabier Judez et al. J. Phys. Chem. Le�. 2017, 8, 1956−1960
1,0 1,5 2,0 2,5 3,0
-0,3
-0,2
-0,1
0,0
0,1
0,2
0,3
0,4
2,42V
1st cycle
3rd cycle
I (m
A)
Ecell [V]
Cyclic voltamperometry
Li/ SPE/ 30%S Cathode, 70ºC
2,48V
2,25V
2,05V
11
Al CC in LiTFSI/PEO based Li-S cell
Effect of salt (LiTFSI vs. LiFSI)33
Li/SPE(LiFSI or LiTFSI)/Li
symmetric cell at 70ºC,
collected after several static
standing periods of time
12Xabier Judez et al. J. Phys. Chem. Le�. 2017, 8, 1956−1960
PEO/LiFSI PEO/LiTFSI
PS dissolved in
polymer electrolyte
Effect of salt (LiTFSI vs. LiFSI)33
Xabier Judez et al. J. Phys. Chem. Le�. 2017, 8, 1956−196013
Effect of S% and thickness in the cathode for LiFSI/PEO cells
Cathode effect in LiFSI LiS cells33
50% S, C/20C/20
14Xabier Judez et al. J. Phys. Chem. Le�. 2017, 8, 1956−1960
Long term stability, optimized 40%S cathode, running experiments
33 Cathode effect in LiFSI LiS cells
LiFSI/PEO, 40%S, @70ºC LiFSI/PEO, 40%S, @70ºC
0,1
0,2
0,3
0,4
0,5
0,6
0,7
Dis
. C
ap
/ m
Ah
cm-2
C/20
C/10
200
400
600
800
Dis. cap.
Dis
. C
ap
/ m
Ah
g-1
80
90
100
110
Coulomb. ef
Co
ulo
mb
. e
f./
%
C/10
C/20
0 100 200 300 400 500 600
0
200
400
600
800
1000
Dis
. C
ap
/ m
Ah
g-1
Cycle/ Cycle n.
Dis. Cap.
Columbic ef.
70
80
90
100
110
C/20
C/10
Co
ulu
mb
. e
f. / %
C/2
C/5
C/10
30%S, LiFSI, 70ºC, Reference cell. C rate test
15
0 50 100 150 200 250 300 350 4000,0
0,1
Dis. cap.
Cycle/ Cycle no.
0 50 100 150 200 250 300 350 4000
Cycle/ Cycle no.
70
Approaches to improve S utilisation and areal capacity, based on electrolyte
Composite electrolyte concepts33
16
Al2O3
Ohara, LICGCTM
Garnet LGLZO
Ionic conductivity
Composite electrolyte concepts33
17
Sample TLi+
[1] Sample TLi+
[1]
FSI 0,13 FSI 0,13
3.1 v% Ohara FSI 0,19 3,1 v% Al2O3
FSI 0,15
10 v% Ohara FSI 0,19 10 v% Al2O3
FSI 0,14
20 v% Ohara FSI 0,1620 v% Al
2O3
FSI0,11
[1] Evans, J.; Vincent, C. A.; Bruce, P. G. Polymer 1987, 28, 2324-2328. Watanabe et al. Solid State Ionics
1988, 28, 911-917.
Stability vs. Li (Li/SPE/Li tests, 70ºC, 0.1 mA/cm2)
Composite electrolyte concepts33
Static Li/SPE/Li test, 70ºC, EIS measurements every 4 hours
18
PEO/LiTFSI
PEO/LiFSI
PEO/LiFSI 10%vol Ohara
PEO/LiFSI 10%vol Al2O3
PEO/LiFSI 3.1%vol Al2O3
Effect of filler nature
600
800
1000
1200
Ref. Cell
3.1 v% Ohara
3.1 v% Al2O3
Dis
. C
ap
/ m
Ah
g-1
40
60
80
100
C/10
C/5
Co
ulo
mb
. e
f./
%
C/10
C/20
0,6
0,8
1,0
1,2
1,4 Ref. Cell
3.1 v% Ohara
3.1 v% Al2O3
Dis
. C
ap
/ m
Ah
cm
-2
C/20
C/10
C/5C/10
Composite electrolyte concepts33
19
0 10 20 30 40 500
200
400
Dis
. C
ap
Cycle/ Cycle no.
0
20
40
C/2 Co
ulo
mb
. e
f./
%
0 10 20 30 40 500,0
0,2
0,4
Dis
. C
ap
Cycle/ Cycle no.
C/2
Composite electrolyte concepts33
Lithium anode
PEO+3.1v% Al2O3
Sulfur cathode
PEO+3.1v% Ohara
1,0
1,2
3.1 v% Ohara
3.1 v% Al2O3
C/20110
Sandwich configuration
1,0
1,2Comparison
Reference
3.1 v% Sandwich
110
20
0 10 20 30 40 500,0
0,2
0,4
0,6
0,8
1,0 3.1 v% Al2O3
Dis
. C
ap
/ m
Ah
cm-2
Cycle/ Cycle no.
C/10
C/5
C/2
C/10
70
80
90
100
Co
ulo
mb
. ef.
/%
0 10 20 30 40 500,0
0,2
0,4
0,6
0,8
1,0
C/10
C/2
C/5
C/10
Dis
. C
ap
/ m
Ah
cm-2
Cycle/ Cycle n.
3.1 v% Sandwich
C/20
70
80
90
100
Co
ulo
mb
. e
f. /
%
Composite electrolyte concepts33
Back to LiTFSI…. 40% S cathode, 70ºC
First cycle, C/20
21
Approaches to improve S utilisation and areal capacity, based on electrolyte
Novel electrolyte materials33
22
PEOJeffamine based
SIC hybrids
Garnets
Highly conductive Jeffamine® based polymer electrolytes
-5,0
-4,5
-4,0
-3,5
-3,0
-2,5
Jeff2k:LiFSI (20:1)
Jeff2k:LiFSI (15:1)
Jeff2k:LiFSI (10:1)
Jeff2k:LiTFSI(20:1)
log
s
-5
-4
-3
Jeff1k(20:1)
Jeff1k(15:1) Jeff1k(10:1)
Jeff2k(20:1)
Jeff2k(15:1)
log σ
(S
·cm
-1)
60ºC
70ºC 25ºCEffect of Jeffamine Mw, LiTFSI
Novel electrolyte materials33
Itziar Aldalur et al. Journal of Power Sources 347 (2017) 37-46
2,6 2,7 2,8 2,9 3,0 3,1 3,2 3,3 3,4
-6,5
-6,0
-5,5 Jeff2k:LiTFSI(20:1)
Jeff2k:LiTFSI(15:1)
Jeff2k:LiTFSI(10:1)
PEO:LiTFSI(20:1)
PEO:LiFSI (20:1)
1000/T
2,6 2,8 3,0 3,2 3,4
-6
Jeff2k(15:1)
Jeff2k(10:1) Jeff600(20:1)
PEO(20:1)
1000/T(K)
I. Aldalur et al. To be published
Compound Salt composition
[EO:TFSI]
T+
Jeffamine M-2070
20:1 0.16
15:1 0.25
10:1 0.38
Jeffamine M-1000
20:1 0.21
15:1 0.17
10:1 0.27
Effect of salt (LiTFSI vs. LiFSI)
23
Nanohybrid polymer electrolytes –pure anion and solvating
segments
SiO2
(10 nm)
Al2O3
(10 nm)
Al2O3
(5 nm)
Novel electrolyte materials33
N. Lago, O. Garcia-Calvo, J.M. Lopez del Amo,T. Rojo and Michel Armand, ChemSusChem, 10.1002/cssc.201500783
M. Armand, I. Villaluenga; T. Rojo; WO 2014/012679 A124
Novel electrolyte materials33
Li7-3x
Gax□2x
La3Zr
2O
12
GARNETS LLZO
25 Lucienne Buannic, et al., Chem. Mater, 29, 4, (2017)
The dual
substitution
strategy leads to an
increase in σLi+and
a decrease in
activation energy
• LiFSI/PEO is a path towards stable polymer Li-S cells with a simple &
low cost configuration
• Ohara as filler enhances initial areal capacity and S utilisation.
Al2O
3stabilises Li metal-electrolyte interface
Sandwich configuration improves Coulombic efficiency
• Nature and size of inorganic fillers plays a significant role yet to be
understood.
Conclusions44
26
Future work
• Ongoing work to increase S content in solid cathodes
• Detailed analysis of interactions & interfaces in process
• Processing optimisation
• Better polymers for fast cycling towards RT operation
Acknowledgements55
Basque Government (PhD grant
X. Judez, Berrikertu, Elkartek16)
Spanish Government (MINECO
RETOS Ref: ENE2015-64907-C2-
1-R, Juan de la Cierva C. Li)
CIC team (missing many)!
27
Prof. Zibin Zhou
Prof. Jose Antonio Gonzalez Marcos
Thank you!
Muchas gracias!
Eskerrik asko!!!
28