International Battery Association (IBA) 2013 Meeting , Barcelona, Spain

March 13, 2013

Development of all-solid-state lithium batteries

with sulfide solid electrolytes

Akitoshi Hayashi and Masahiro Tatsumisago

(Osaka Prefecture University, Japan)

Osaka Prefecture University

Outline

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

Osaka Prefecture University

Demand for all-solid-state battery

Organic liquid electrolyte
anode
C

anode

cathode

Co O 2

Li+ Li+ Li+

Li+
XLi+ Li+
Li+ Li+
X- Li+
Li+ Li+

Inorganic solid electrolyte

cathode
X-

Lithium-ion battery

remove safety hazards of

leakage, volatilization and
flammability

+
Li+ Li+ Li Li+ Li+ Li+
+
+
L i + L i L iL+i
Li+ Li+

all-solid-state battery

innovative battery for

the next generation
high safety
long cycle life
high energy density
Serious safety problems become
obvious and thus improving safety of
stacked battery
possibility of use of high
batteries (especially large-sized
capacity electrodes
batteries) is a big issue to be solved.
Stacked high voltage Li metal, elemental S
Osaka Prefecture University

Two types of all-solid-state rechargeable lithium batteries

Li / LiPON / LiCoO2

Thin-film battery
Negative Electrode

Solid Electrolyte

Long cycle performance

10 m

Substrate
Positive Electrode
Data from the web site of Excellatron

Bulk-type battery

Consisting of powder-compressed layers

of electrode and electrolyte

Negative
Electrode
Solid
Electrolyte
Positive
Electrode
Electrode Material

1mm

high energy density !

Key points:

1. Solid electrolytes with high conductivity

2. Favorable contact at solid-solid interface
Conductive additive Solid Electrolyte

Osaka Prefecture University

Why inorganic solid electrolytes?

Merits of inorganic solid electrolytes

charge-transfer reaction at electrode

Single cation conduction

Wide electrochemical window
Simple electrochemical reactions

(Li / electrolyte)

xLi2S(100-x)P2S5 glass in EC+DEC

K. Minami et al., Solid State Ionics, 192, 122 (2011).

M. Chiku et al., Electrochemistry, 80, 740 (2012).

Why sulfide glass solid electrolytes?

Superionic phase

High ionic conductivity

Easy reduction of grain-boundary resistances
Wide selection of compositions
Superionic crystalline phases are easily
precipitated from glass.

Cross-sectional SEM images of compressed powder pellets

Sulfide glass electrolyte

Li2S-P2S5

Ionic conductivity

Advantages of sulfide glass electrolytes

Oxide crystalline electrolyte

Li7La3Zr2O12

20 m
Li+ = 10-3 S cm-1

20 m
Li+ = too small (< 10-7 S cm-1)

(sintered pellet: 10-4 S cm-1)

Glass

Crystal

Composition

Easy deformation of
sulfide electrolytes is
useful for achieving
favorable
interface
between electrode and
electrolyte.

Precipitation of superionic Li7P3S11 phase from the 70Li2S30P2S5 (mol%) glass

Solid-state
reaction

550 oC

360 oC
240 oC
glass

10

15

20
25
30
o
2 / (CuK)

35

40

Conductivity / S cm

: Li4P2S6

Intensity (arb.unit)

: Li3.2P0.96S4
: Li7P3S11
: Li3PS4

-1

10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
-8
10
-9
10
1.8

360 o C

240 o C

glass
550 o C
Solid-state reaction
2

2.2 2.4 2.6 2.8

3.2 3.4

1000 T -1 / K -1
The formation of a superionic
metastable phase is responsible
for increasing conductivity of
glass-based solid electrolytes.

F. Mizuno et al., Adv. Mater., 17, 918 (2005); Solid State Ionics., 177, 2721 (2006). Osaka

Prefecture University

Solid electrolytes with high lithium ion conductivity

Li10GeP2S12 crystal
25= 1.2 x 10-2 Scm-1

Li7P3S11 glass-ceramic
25= 1 x 10-2 Scm-1

Kamaya, Kanno et al, Nat. Mater.,

10, 682 (2011).

Conductivity / S cm-1

10

10

-1

10

-2

Temperature ( oC )
200
100
25

300

Li1.3Al0.3Ti1.7(PO4)3 crystal
Li2S-SiS2-P2S5-LiI glass

10

-5

10 -6
1.5

Li3.25P0.75Ge0.25S4
thio-LISICON II

Liquid electrolytes

Li7P3S11 glass-ceramic
25= 5 x 10-3 Scm-1
Adv. Mater., 17, 918 (2005).
J. Non-Cryst. Solids, 356, 2670 (2010).

10 -3
10 -4

Seino et al., 36th Solid

State Ionics Meeting
in Japan (2010).

Li3.4V0.4Ge0.6O4
crystal

Li3N crystal
La0.51Li0.34TiO2.94 crystal

Li2O-Nb2O5 glass
Li2O-B2O3-LiCl glass

Li3.3PO3.8N0.22 glass (LiPON)

2.5
3
1000 T-1 / K-1

3.5

T. Minami ed., Solid State Ionics for Batteries, Springer, Tokyo, p. 1 (2005).

Li+ ion conductivity of the

sulfide solid electrolytes
is now higher than that of
liquid electrolytes!

Osaka Prefecture University

Chemical stability in air of sulfide electrolytes

PS43

PS43

2.5

S
PS43

600

500
400
300
Wavenumber / cm -1

200

H2S generation

(R.H. 50%)

1.5
1
0.5
0

before

700

H2S amount / cm3 g-1 (1min)

Intensity (arb. unit)

after exposure
to air for 1day

Li2S-P2S5 glasses

75Li2S25P2S5 glass

60

70

80
Mol % Li 2S

90

100

Main structural unit (PS43-) did not

change after exposure to air for 1day.

Hydrolysis is suppressed.

Sulfide solid electrolytes with moderate chemical stability in air atmosphere

are prepared by selecting compositions.
H. Muramatsu et al., Solid State Ionics, 182 (2011) 116.

Osaka Prefecture University

Outline

10

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

Osaka Prefecture University

Application to bulk-type all-solid-state batteries

Stainless-steel
(current collector)

Working electrode: e.g. Li4Ti5O12

Solid electrolyte (SE):
Li2S-P2S5 glass-ceramic

Polycarbonate
(insulator)

screw

Composite electrode

Li+

eSE

active material

Counter electrodeLi-In alloy

(reference electrode)

The formation of Li+ and econduction paths to active

material particles is significant.

conductive additive = 60 : 40 : 4 (wt %)

Osaka Prefecture University

11

Electrochemical performance of bulk-type solid-state batteries

Li-In / 70Li2S29P2S51P2S3 glass-ceramic / Li4Ti5O12

100 oC
12.8

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.
K. Minami et al., Solid State Ionics, 192 (2011) 122.

Osaka Prefecture University

12

Approaches to fabricate favorable electrode-electrolyte interfaces

13

Li / S
batteries

M. Tatsumisago, M. Nagao, A. Hayashi.

Journal of Asian Ceramic Societies, in press.

Sulfide electrolyte coating on LiCoO2 electrode by PLD

KrF excimer laser
= 248 nm

14

Surface coating using PLD

Li2S-P2S5 target
(80Li2S20P2S5)

KrF Excimer laser

(248 nm)
Vacuum chamber

Ar filled glove box

Deposition conditions
Target

Pellet of mixture of Li2S

vibrator

and P2S5 crystalline powder

80Li2S20P2S5 mol%
Ambient gas

Ar gas (5 Pa)

Temperature

Room temperature

Frequency

10 Hz

Laser fluence

2 J cm-2

Target-substrate distance 7 cm

PLD
LiNbO3-coated
LiCoO2*

Li2S-P2S5 electrolyte

* N. Ohta, K. Takada et al. Electrochem. Commun. 9, 1486 (2007).

All-solid-state cells using SE-coated LiCoO2

5

LiCoO2 positive
electrode
Cell voltage / V

Li2S-P2S5 electrolyte

Cross-sectional SEM image

LiCoO2

LiCoO2

Li2S-P2S5

In / Li2S-P2S5 / LiCoO2
0.13 mA cm-2

With SE particles
With SE coatings

0
20
40
60
80 100 120
-1
Capacity / mAh g (LiCoO2+Li2S-P2S5)

LiCoO2
LiCoO2

5 m

Lithium-ion conducting paths are formed

with small amounts of solid electrolytes.

With SE particles
With SE coatings
(30 wt% SE particles
(10 wt% SE films
were mixed)
were coated)
A. Sakuda et al, J. Power Sources, 196 (2011) 6735.

15

All-solid-state Li / S batteries
abundant element
large theoretical capacity
(1672 mAh g-1)

S+

xLi+

xe-

discharge
charge

LixS

Li-In / 80Li2S20P2S5 (SE) / 25S25AB50SE (wt%)

Cell potential vs. Li / V

Sulfur active material

16

In / LiCoO2

charge

discharge

1
0

Li-In / S

25oC
0.064 mA cm-2

400

800

1200

1600

Capacity / mAh g-1

Sulfur positive electrode in all-solid-state cells shows a good cycle performance.

M. Nagao, A. Hayashi, M. Tatsumisago, Electrochim. Acta, 56, 6055 (2011).

Increase of the sulfur content in a positive electrode

Li-In / SE / 50S20AB30SE (wt%)

17

C; blue, P; green, S; red

Ball-milling the S-AB composite at 155oC

(the lowest viscosity coefficient of sulfur)

Capacity / mAh g-1 (sulfur)

1400
1200
1000

0.064
mA cm-2

0.064 mA cm-2

800
600

200 nm

Cross-sectional
EELS mapping

400
200
0

25
0

0.64

oC

10

mA cm-2

20
30
Cycle number

Li e

(0.2 C)
40

AB

Li

sulfur

50

Energy density based on the weight of the total

positive electrode is increased (1007 Wh kg-1).
Sulfur with the size less than 200 nm and AB
particles are homogeneously dispersed in the SE
matrix.
large capacity & good cyclability

e
e Li
e

Li

Li2S-P2S5
SE

M. Nagao et al., Energy Technology, in press.

Outline

18

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

Osaka Prefecture University

Why Na batteries?
Na+ ion batteries

19

Next-generation batteries
with high energy density
using abundant sodium
sources
*J.O. Besenhard and M. Winter, CHEMPHYSCHEM, 3, 155 (2002).

Sodium-sulfur (NAS) batteries

Large energy density (760 Wh kg-1)

Na / sintered -alumina / S
(liquid)
(solid)
(liquid)

High-temperature operation (300 oC)

Strict security apparatus
Limitation of usage environment

All-solid-state Na/s batteries operating at room temperature are

strongly desirable from safety point of view.
New solid electrolytes suitable for solid-state batteries
Osaka Prefecture University

New Na+ ion conducting sulfide electrolytes

20

75Na2S25P2S5 (mol%) = Na3PS4

Conductivity

-1

Conductivity / S cm

-1

10

XRD

Glass-ceramic

-2

10

-3

10

-4

10

-5

10

Glass

-6

10

2.5

1000 T-1 / K-1

3.5

Conductivity increases by crystallization

of the Na3PS4 glass.
25 = 210-4 S cm-1
A. Hayashi et al., Nature Communications, 3 (2012) 856.

A cubic Na3PS4 phase, which has not

been reported, is precipitated in
the glass-ceramic electrolyte.
Osaka Prefecture University

Application to all-solid-state sodium batteries

Stainless steel
(current collector)

Solid electrolyte (SE):

cubic-Na3PS4
glass-ceramic
Counter/reference
electrode:
Na-Sn alloy

Cell potential vs. Na-Sn / V

Working electrode:
TiS2SE=2:3
(wt ratio)

Na-Sn / Na3PS4 / TiS2

25 oC, 0.013 mA cm-2, 1.17-2.40 V

The all-solid-state sodium battery with the Na3PS4 electrolyte is

charged and discharged for 10 cycles and shows a good cycleability
at room temperature.
A. Hayashi et al., Nature Communications, 3 (2012) 856.

Osaka Prefecture University

21

Summary
1. Sulfide glass-based materials have favorable properties as solid
electrolyte for bulk-type all-solid-state batteries. Especially, the glassceramics 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 been
developed 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 electrolyte
operate at room temperature.

Acknowledgements
This work was financially supported by
Grant-in-Aid for Scientific Research from MEXT
CREST and ALCA projects from JST
Toyota Motor Co.