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 Li+ Li+ X-

Inorganic solid electrolyte

anode cathode
+ Li+ Li+ Li Li+ Li+ Li+ + +i + L i + L i L iL Li+ Li+

cathode
Co O 2

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

remove safety hazards of leakage, volatilization and flammability

Lithium-ion battery

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 Thin-film battery

Solid Electrolyte Negative Electrode
10 m

Li / LiPON / LiCoO2

Long cycle performance

Substrate Positive Electrode

Bulk-type battery
Negative Electrode Solid Electrolyte Positive Electrode Electrode Material
1mm

Data from the web site of Excellatron

Consisting of powder-compressed layers of electrode and electrolyte

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
Single cation conduction Wide electrochemical window Simple electrochemical reactions
charge-transfer reaction at electrode

(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?

Advantages of sulfide glass electrolytes
Ionic conductivity

Superionic phase Glass

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

Crystal

Cross-sectional SEM images of compressed powder pellets Sulfide glass electrolyte

Oxide crystalline electrolyte

Composition

Li2S-P2S5

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)

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

: Li3.2P0.96S4 : Li7P3S11 : Li3PS4 : Li4P2S6
10 -1 10 -2 10 -3 10 -4 10 -5 10 -6 10 -7 10 -8 10 -9 10 1.8
0

-1

Conductivity / S cm

Solid-state reaction

360 o C

240 o C

Intensity (arb.unit)

glass 550 o C Solid-state reaction 2 2.2 2.4 2.6 2.8 3 3.2 3.4

550 oC

360 oC 240 oC glass

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

10

15

20 25 30 o 2 / (CuK )

35

40

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

Solid electrolytes with high lithium ion conductivity

Li10GeP2S12 crystal 25= 1.2 x 10-2 Scm-1
Kamaya, Kanno et al, Nat. Mater., 10, 682 (2011).

Li7P3S11 glass-ceramic 25= 1 x 10-2 Scm-1 0

Seino et al., 36th Solid State Ionics Meeting in Japan (2010).

10 Conductivity / S cm-1 10 10

300

Temperature ( oC ) 200 100 25

Li2S-SiS2-P2S5-LiI glass Li3.25P0.75Ge0.25S4 thio-LISICON II

Li1.3Al0.3Ti1.7(PO4)3 crystal

-1 -2

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 10
-5
Li2O-Nb2O5 glass

Li3.4V0.4Ge0.6O4 crystal Li2O-B2O3-LiCl glass Li3.3PO3.8N0.22 glass (LiPON)

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

10 -6 1.5

2.5 3 1000 T-1 / K-1

3.5

Li+ ion conductivity of the sulfide solid electrolytes is now higher than that of liquid electrolytes!

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

Osaka Prefecture University

Chemical stability in air of sulfide electrolytes

75Li2S25P2S5 glass S S P S
PS43

Li2S-P2S5 glasses
2.5

Intensity (arb. unit)

after exposure to air for 1day PS43

PS43

H2S amount / cm3 g-1 (1min)

2 1.5 1 0.5 0 60 70

H2S generation
(R.H. 50%)

before

700

600

500 400 300 Wavenumber / cm -1

200

Main structural unit (PS43-) did not change after exposure to air for 1day.

80 Mol % Li 2S

90

100

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

11

Stainless-steel (current collector)

Working electrode: e.g. Li4Ti5O12 Solid electrolyte (SE): Li2S-P2S5 glass-ceramic Counter electrodeLi-In alloy (reference electrode)

Polycarbonate (insulator) Li+

screw

Composite electrode
The formation of Li+ and econduction paths to active material particles is significant.

eSE active material

conductive additive = 60 : 40 : 4 (wt %) Osaka Prefecture University

Electrochemical performance of bulk-type solid-state batteries

Li-In / 70Li2S29P2S51P2S3 glass-ceramic / Li4Ti5O12

12

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

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

Target

Ar filled glove box

Pellet of mixture of Li2S and P2S5 crystalline powder 80Li2S20P2S5 mol%

Deposition conditions

vibrator
PLD
LiNbO3-coated LiCoO2*

Ambient gas Temperature Frequency Laser fluence

Ar gas (5 Pa) Room temperature 10 Hz 2 J cm-2

Li2S-P2S5 electrolyte

Target-substrate distance 7 cm

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

All-solid-state cells using SE-coated LiCoO2

LiCoO2 positive electrode
Cell voltage / V 5

15

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

Li2S-P2S5 electrolyte

With SE particles With SE coatings

Cross-sectional SEM image

LiCoO2 Li2S-P2S5

LiCoO2

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.

All-solid-state Li / S batteries Sulfur active material

abundant element large theoretical capacity (1672 mAh g-1)

16

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

Cell potential vs. Li / V

4 3 2 1 0 0

In / LiCoO2 charge discharge

25oC 0.064 mA cm-2

Li-In / S

S+

xLi+

xe-

discharge charge

LixS

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%) 1400 Capacity / mAh g-1 (sulfur) 1200 1000 800 600 400 200 0 0 25
oC

17

C; blue, P; green, S; red

Ball-milling the S-AB composite at 155oC (the lowest viscosity coefficient of sulfur)

0.064 mA cm-2

0.064 mA cm-2 200 nm

Cross-sectional EELS mapping AB sulfur

0.64 10

mA cm-2

(0.2 C) 40 50

Li e Li e e Li e Li

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

20 30 Cycle number

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

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

19

Sodium-sulfur (NAS) batteries Na / sintered -alumina / S (liquid) (solid) (liquid)

Large energy density (760 Wh kg-1) 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

75Na2S25P2S5 (mol%) = Na3PS4
10 10 10 10 10 10
-1

20

Conductivity

XRD

Conductivity / S cm

-1

-2

Glass-ceramic

-3

-4

-5

Glass
2

-6

1000 T-1 / K-1

2.5

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)

21

Na-Sn / Na3PS4 / TiS2 Cell potential vs. Na-Sn / V

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

Working electrode: TiS2SE=2:3 (wt ratio) Solid electrolyte (SE): cubic-Na3PS4 glass-ceramic Counter/reference electrode: Na-Sn alloy

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

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.