7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 1/22
Akitoshi Hayashi and Masahiro Tatsumisago
(Osaka Prefecture University, Japan)
Osaka Prefecture University
Development of all-solid-state lithium batterieswith sulfide solid electrolytes
International Battery Association (IBA) 2013 Meeting , Barcelona, Spain March 13, 2013
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 2/22
2Outline
Osaka Prefecture University
1. Background
Motivation of all-solid-state rechargeable batteries
2. Sulfide glass solid electrolytes
3. All-solid-state Li batteries with sulfide electrolytes
Approaches to fabricate favorable electrode-electrolyte interfaces
4. Na+ ion conductors for all-solid-state Na batteries
5. Summary
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 3/22
3
Organic liquid electrolyte
L i+L i+
L i+L i+
L i+
L i+
L i+
X -
X -
X -
L i+L i+
L i+L i+
anode
C CoO 2
cathode
Osaka Prefecture University
Demand for all-solid-state battery
Serious safety problems becomeobvious and thus improving safety ofbatteries (especially large-sizedbatteries) is a big issue to be solved.
Lithium-ion battery
innovative battery forthe next generation
Inorganic solid electrolyte
L i+L i+
L i+
L i+
L i+
L i+L i+
L i+
L i+
L i+ L i+ L i+
cathode
all-solid-state battery
anode
remove safety hazards ofleakage, volatilization andflammability
Stacked → high voltage
○high safety○long cycle life○high energy density・stacked battery・possibility of use of high
capacity electrodes
(Li metal, elemental S )
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 4/22Osaka Prefecture University
Solid Electrolyte
Substrate
Negative Electrode
Positive Electrode
Thin-film battery
10m
Bulk-type battery
Positive
Electrode
Solid
Electrolyte
Negative
Electrode
1mm
Electrode Material Conductive additive Solid Electrolyte
Consisting of powder-compressed layersof electrode and electrolyte
high energy density !
Key points:1. Solid electrolytes with high conductivity2. Favorable contact at solid-solid interface
Li / LiPON / LiCoO2
Data from the web site of Excellatron
Long cycle performance
Two types of all-solid-state rechargeable lithium batteries 4
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 5/22
Merits of inorganic solid electrolytes
○Single cation conduction
○Wide electrochemical window
○Simple electrochemical reactions
Why inorganic solid electrolytes? 5
in EC+DECxLi2S・(100-x)P2S5 glass
M. Chiku et al., Electrochemistry, 80, 740 (2012).
(Li / electrolyte)
K. Minami et al., Solid State Ionics, 192, 122 (2011).
charge-transfer reaction at electrode
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 6/22
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 7/22
10-9
10-8
10-7
10-6
10-5
10-4
10-3
10-2
10-1
100
1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4
C o n d u c t i v
i t y / S c m - 1
1000 T-1 / K -1
240 oC360 oC
Solid-state reaction
550 oC
glass
10 15 20 25 30 35 40
I nt e n
sit
y( a
rb . u nit)
2 /o
(CuK)
glass
240 oC
360 oC
550 oC
Solid-state
reaction: Li7P3S11
: Li3.2P0.96S4 : Li4P2S6
: Li3PS4
7
F. Mizuno et al., Adv. Mater ., 17, 918 (2005); Solid State Ionics., 177, 2721 (2006). Osaka Prefecture University
Precipitation of superionic Li7P3S11 phase from the 70Li2S・30P2S5 (mol%) glass
The formation of a superionicmetastable phase is responsiblefor increasing conductivity ofglass-based solid electrolytes.
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 8/22
Liquid electrolytes
C
vty/Scm-
Temperature ( oC )
Li2O-B2O3-LiCl glass
Li2O-Nb2O5 glass
Li3.4V0.4Ge0.6O4
crystal
La0.51Li0.34TiO2.94 crystal
Li3N crystal
Li2S-SiS2-P2S5-LiI glass
Li1.3 Al0.3Ti1.7(PO4)3 crystal
Li3.3PO3.8N0.22 glass (LiPON)
1000 T-1 / K-1
25 100 200 300 0
1.5 2 2.5 3 3.5
10 0
10 -1
10
-2
10 -3
10 -5
10 -4
10 -6
Li3.25P0.75Ge0.25S4
thio-LISICON II Li7P3S11 glass-ceramic25= 5 x 10-3 Scm-1
Li+ ion conductivity of the
sulfide solid electrolytesis now higher than that ofliquid electrolytes!
Li7
P3
S11
glass-ceramic
25= 1 x 10-2 Scm-1
Seino et al., 36th Solid State Ionics Meetingin Japan (2010).
Li10GeP2S12 crystal
Kamaya, Kanno et al, Nat. Mater.,10, 682 (2011).
25= 1.2 x 10-2 Scm-1
8Solid electrolytes with high lithium ion conductivity
T. Minami ed., “Solid State Ionics for Batteries”, Springer, Tokyo, p. 1 (2005).
Adv. Mater., 17, 918 (2005).
J. Non-Cryst. Solids, 356, 2670 (2010).
Osaka Prefecture University
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 9/22
0
0.5
1
1.5
2
2.5
60 70 80 90 100
Mol % Li2S
H 2
S a m o u n t / c m
3 g
- 1 ( 1
m i n )
200300400500600700
I n t e n s i t y ( a
r b .
u n i t )
Wavenu mber / cm -1
PS43
75Li2S・25P2S5 glass
before
PS43
PS43 S S
S
S
P
Main structural unit (PS43-) did not
change after exposure to air for 1day.
after exposureto air for 1day
Chemical stability in air of sulfide electrolytes
Osaka Prefecture UniversityH. Muramatsu et al., Solid State Ionics, 182 (2011) 116.
Hydrolysis is suppressed.
H2S generation(R.H. 50%)
Sulfide solid electrolytes with moderate chemical stability in air atmosphere
are prepared by selecting compositions.
9
Li2S-P2S5 glasses
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 10/22
10Outline
Osaka Prefecture University
1. Background
Motivation of all-solid-state rechargeable batteries
2. Sulfide glass solid electrolytes
3. All-solid-state Li batteries with sulfide electrolytes
Approaches to fabricate favorable electrode-electrolyte interfaces
4. Na+ ion conductors for all-solid-state Na batteries
5. Summary
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 11/22
11
Li2S-P2S5 glass-ceramic
Stainless-steel(current collector)
Polycarbonate
(insulator)
conductive additiveactive materialSE = 60 : 40 : 4 (wt %)
Composite electrode
Osaka Prefecture University
Solid electrolyte (SE):
Application to bulk-type all-solid-state batteriesApplication to bulk-type all-solid-state batteries
The formation of Li+ and e-
conduction paths to activematerial particles is significant.
Counter electrode:Li-In alloy
(reference electrode)
Working electrode: e.g. Li4Ti5O12
screw
Li+
e-
12
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 12/22
Li-In / 70Li2S・29P2S5・1P2S3 glass-ceramic / Li4Ti5O12
The cell operated at a high current density of 12.8 mA cm-2
and kept the capacity of 130 mAh g-1 for 700 cycles.
Osaka Prefecture University
100 oC
K. Minami et al., Solid State Ionics, 192 (2011) 122.
12Electrochemical performance of bulk-type solid-state batteries
12.8
A h f b i f bl l d l l i f
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 13/22
13Approaches to fabricate favorable electrode-electrolyte interfaces
Li / S
batteries
M. Tatsumisago, M. Nagao, A. Hayashi.
Journal of Asian Ceramic Societies, in press.
14S lfid l l i LiC O l d b PLD
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 14/22
Ar filled glove box
KrF excimer laser
( = 248 nm )
Vacuum chamber
Target Pellet of mixture of Li2S
and P2S5 crystalline powder
(80Li2S・20P2S5 mol%)
Ambient gas Ar gas (5 Pa)
Temperature Room temperature
Frequency 10 Hz
Laser fluence 2 J cm-2
Target-substrate dis tance 7 cm
Deposition conditions
14Sulfide electrolyte coating on LiCoO2 electrode by PLD
vibrator
Li2S-P2S5 electrolyteLiNbO3-coated
LiCoO2*
Li2S-P2S5 target
KrF Excimer laser(248 nm)
Surface coating using PLD
PLD
(80Li2S・20P2S5)
* N. Ohta, K. Takada et al. Electrochem. Commun. 9, 1486 (2007).
All s lid st t lls si SE t d LiC O 15
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 15/22
LiCoO2 positiveelectrode
Li2S-P2S5 electrolyte
All-solid-state cells using SE-coated LiCoO2
A. Sakuda et al, J. Power Sources, 196 (2011) 6735.
1
2
3
4
5
0 20 40 60 80 100 120
C e l l v o l t a g e / V
Capacity / mAh g-1
(LiCoO2+Li
2S-P
2S
5)
With SE particles
With SE coatings
With SE particles(30 wt% SE particleswere mixed)
With SE coatings(10 wt% SE filmswere coated)
In / Li2S-P2S5 / LiCoO2
0.13 mA cm-2
Lithium-ion conducting paths are formedwith small amounts of solid electrolytes.
5 m
LiCoO2
LiCoO2
LiCoO2
Li2S-P2S5
LiCoO2
Cross-sectional SEM image
15
All lid t t Li / S b tt i
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 16/22
Sulfur positive electrode in all-solid-state cells shows a good cycle performance.
All-solid-state Li / S batteries 16
M. Nagao, A. Hayashi, M. Tatsumisago, Electrochim. Acta, 56, 6055 (2011).
In / LiCoO2
25
o
C0.064 mA cm-2
2
1
0
3
4
5
0 400 800 1200 1600
C e l l p o t e
n t i a l v s . L i / V
Capacity / mAh g-1
Li-In / S
charge
discharge
S + xLi+ + xe- LixSdischarge
charge
Sulfur active material・abundant element・large theoretical capacity
(1672 mAh g-1)
Li-In / 80Li2S・20P2S5 (SE) / 25S・25AB・50SE (wt%)
I f th lf t t i iti l t d
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 17/22
Li-In / SE / 50S・20AB・30SE (wt%)
25 oC
0.064 mA cm-2
0.64 mA cm-2 (0.2 C)
0.064
mA cm-2
0 10 20 30 40 500
200
400
600
800
1000
1200
1400
Cycle number
C a p a c i t y
/ m A h g - 1
( s u l f u r )
17
M. Nagao et al., Energy Technology, in press.
Increase of the sulfur content in a positive electrode
Ball-milling the S-AB composite at 155oC(the lowest viscosity coefficient of sulfur)
200 nm
C; blue, P; green, S; red
e-
e-
e-
Li+
e-
Li+
Li+
Li+
AB
sulfur
Li2S-P2S5
SE
Cross-sectional
EELS mapping
・Energy density based on the weight of the totalpositive electrode is increased (1007 Wh kg-1).
・Sulfur with the size less than 200 nm and ABparticles are homogeneously dispersed in the SEmatrix. large capacity & good cyclability
18Outline
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 18/22
18Outline
Osaka Prefecture University
1. Background
Motivation of all-solid-state rechargeable batteries
2. Sulfide glass solid electrolytes
3. All-solid-state Li batteries with sulfide electrolytes
Approaches to fabricate favorable electrode-electrolyte interfaces4. Na+ ion conductors for all-solid-state Na batteries
5. Summary
Why Na batteries? 19
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 19/22
Why Na batteries?
Sodium-sulfur (NAS) batteries ・Large energy density (760 Wh kg-1)・High-temperature operation (>300 oC)・Strict security apparatus
Na / sintered -alumina / S(liquid) (solid) (liquid)
Limitation of usage environment
Na+ ion batteries
Next-generation batterieswith high energy densityusing abundant sodium
sources
19
*
*J.O. Besenhard and M. Winter, CHEMPHYSCHEM , 3, 155 (2002).
All-solid-state Na/s batteries operating at room temperature arestrongly desirable from safety point of view.
New solid electrolytes suitable for solid-state batteries
Osaka Prefecture University
New Na+ ion conducting sulfide electrolytes 20
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 20/22
10-6
10-5
10-4
10-3
10-2
10-1
2 2.5 3 3.5
C o
n d u c t i v i t y / S
c m - 1
1000 T-1 / K-1
Glass
Glass-ceramic
75Na2S・25P2S5 (mol%) = Na3PS4
Conductivity increases by crystallizationof the Na3PS4 glass.
A. Hayashi et al., Nature Communications, 3 (2012) 856.
New Na ion conducting sulfide electrolytes 20
A cubic Na3PS4 phase, which has notbeen reported, is precipitated inthe glass-ceramic electrolyte.
XRDConductivity
25 = 2×10-4 S cm-1
Osaka Prefecture University
Application to all solid state sodium batteries 21
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 21/22
The all-solid-state sodium battery with the Na3PS4 electrolyte ischarged and discharged for 10 cycles and shows a good cycleability
at room temperature.
25 oC, 0.013 mA cm-2, 1.17-2.40 V
C e l l p o
t e n t i a l v s .
N a - S n / V
cubic-Na3PS4
glass-ceramic
Stainless steel
(current collector)
Solid electrolyte (SE):
Counter/referenceelectrode:Na-Sn alloy
Working electrode:TiS2:SE=2:3
(wt ratio)
Na-Sn / Na3PS4 / TiS2Na-Sn / Na3PS4 / TiS2
Application to all-solid-state sodium batteries 21
Osaka Prefecture UniversityA. Hayashi et al., Nature Communications, 3 (2012) 856.
Summary
7/21/2019 Akitoshi Hayashi
http://slidepdf.com/reader/full/akitoshi-hayashi 22/22
Summary
1. Sulfide glass-based materials have favorable properties as solid
electrolyte for bulk-type all-solid-state batteries. Especially, the glass-ceramics in the system Li2S-P2S5 show high Li+ ion conductivities of 10-3
to 10-2 S cm-1, which are higher than those of liquid electrolytes.
2. Electrochemical performance of all-solid-state Li batteries has beendeveloped by the modification of the electrode-electrolyte interface.
3. Cubic-Na3PS4 glass-ceramic electrolyte with the conductivity of 10-4 S
cm-1 is prepared and all-solid-state Na batteries with the electrolyteoperate at room temperature.
AcknowledgementsThis work was financially supported by・Grant-in-Aid for Scientific Research from MEXT ・CREST and ALCA projects from JST ・Toyota Motor Co.