Solid-State Lithium Batteries Using Glass Electrolytes Masahiro - - PowerPoint PPT Presentation

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Solid-State Lithium Batteries Using Glass Electrolytes Masahiro - - PowerPoint PPT Presentation

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International Workshop on Scientific Challenges on New Functionalities in Glass April 15-17, 2007 Solid-State Lithium Batteries Using Glass Electrolytes Masahiro TATSUMISAGO Department of Applied Chemistry Graduate School of Engineering Osaka

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SLIDE 1

Solid-State Lithium Batteries Using Glass Electrolytes

Masahiro TATSUMISAGO Department of Applied Chemistry Graduate School of Engineering Osaka Prefecture University Japan

International Workshop on Scientific Challenges on New Functionalities in Glass April 15-17, 2007

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SLIDE 2

AGENDA

  • Introduction – Why all-solid-state battery?

Why glass-based electrolytes?

  • Preparation of lithium ion conducting glasses and

glass-ceramics

  • All-solid-state lithium secondary batteries using

Li2S-based glass-ceramics

  • Preparation of glassy electrode materials for all-

solid-state lithium secondary batteries - A new concept of all-glass-based battery systems

  • Conclusions
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SLIDE 3

Introduction

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SLIDE 4

Change of energy density of batteries Development of lithium ion battery market

number amount Number Amount / billion yen

Li-ion Ni-H Ni-Cd Li-ion Ni-H Ni-Cd

Energy density / Wh/L 5 . 2 x d u r i n g 1 5 y e a r s

Li-ion battery Japan China Korea

  • thers

Share of battery in the world

Development of the battery business Development of the battery business

The lithium ion secondary battery is very promising not only for miniaturized electric appliances but also as a large energy storage device for HEV and EV. The lithium ion secondary battery is very promising not only for miniaturized electric appliances but also as a large energy storage device for HEV and EV. Development of miniaturized electric appliances Development of miniaturized electric appliances

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SLIDE 5

All-solid-state lithium secondary battery system using non-flammable inorganic solid electrolytes

Ultimate goal of

rechargeable energy sources ・ high safety ・ high reliability ・ high energy density

There are serious safety problems present in lithium ion secondary batteries using flammable organic liquid electrolytes.

Smart card

Film battery ICAntenna

EV

Studies on all-solid-state lithium secondary battery

Thin-film battery Bulk-type battery

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SLIDE 6

………. very promising for use in all-solid-state batteries

・ wide selection of compositions ・ isotropic properties ・ no grain boundaries ・ easy film formation ・ nonflammability ・ etc.

Inorganic glassy solid electrolytes

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SLIDE 7
  • 2. Single cation conduction is realized because glassy

materials belong to the so-called “decoupled systems” in which the mode of ion conduction relaxation is decoupled from the mode of structural relaxation.

  • 1. Ion conductivity is generally higher in glass than that

in corresponding crystal due to the so-called “open structure.”

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

cathode anode

C CoO2

Inorganic glassy electrolyte

all-solid-state battery

anode cathode

conventional battery crystal glass

Inorganic glassy solid electrolytes

Ideal battery system with no side reactions Large amounts of free volume

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SLIDE 8

Intensity (arb.unit) : α-AgI

σ25 =10-1 Scm-1

  • 3. Superionic coducting crystals

as a metastable phase are easily formed from inorganic glassy electrolytes.

Inorganic glassy solid electrolytes

c r y s t a l g l a s s liquid supercooled liquid

Volume Temperature

Tg Tm

crystallization

S u p e r i

  • n

i c p h a s e

74AgI･26(0.33Ag2O･0.67MoO4)

Tatsumisago et al., NATURE, 354 (1991) 217; Chem. Lett. (2001) 814.

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SLIDE 9

Preparation of lithium ion conducting glasses and glass-ceramics

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SLIDE 10

System Li2S-SiS2 Li-P-O-N Li2S-B2S3 Li4SiO4-Li3BO3 Li2S-P2S5 Li2S-GeS2 Li2S-SiS2-LiI Li2S-P2S5-LiI Li2S-SiS2-Li3PO4 Li2S-SiS2-Li4SiO4 Li2O-Nb2O5 10-6 10-6 10-6 10-3 10-3 10-4 10-3 10-3 10-4 10-4 10-5 Nassau Tatsumisago Bates Ribes Malugani Levasseur Souquet Kennedy Malugani Kondo Tatsumisago σ25 / Scm-1 Researcher

Lithium Ion conducting glassy systems

Twin-roller quenching Twin-roller quenching Sputtering Twin-roller quenching Melt quenching Melt quenching Melt quenching Melt quenching Melt quenching Melt quenching Twin-roller quenching Procedure

High Li+ ion conduction in glass ・ Increase in Li+ ion concentration as much as possible ・ Use of counter anions with high polarizability

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SLIDE 11

10-6 10-5 10-4 10-3 10-2 10-1 100 1 1.5 2 2.5 3 3.5 4

Conductivity / S cm-1 1000 / T (K-1)

Thio-LISICON Li3.25Ge0.25P0.75S4 Perovskite La0.51Li0.34TiO2.94 Li2O-Al2O3-TiO2-P2O5 (OHARA gc) glass-ceramic Li2S-SiS2–P2S5-LiI glass LISICON Li14Zn(GeO4)4 NASICON Li1.3Al0.3Ti1.7(PO4)3 Li3N Li3.4V0.4Ge0.6O4 Li2O-Nb2O5 glass Li2O-B2O3-LiI glass Li2S-SiS2 glass Li2S-SiS2-Li4SiO4 glass

Li2S-P2S5 glass-ceramics σ25=3.2x10-3 Scm-1

Advanced Materials 17 (2005) 918.

Temperature dependence of conductivity of a variety of high lithium ion conducting materials

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

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SLIDE 12

・ Room temperature process ・ Obtaining fine powders directly Mechanochemical synthesis

pulverization chemical reaction Mechanical energy

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。

Centrifugal force Rotation of base disk Rotation of pot Ball

Planetary ball mill Mechanochemical preparation of 95(0.6Li2S・0.4SiS2)・5Li4SiO4 glass

2.0 2.5 3.0 3.5 Conductivity / S cm-1

10h,20h 5h 1h 0h

10-2 100 10-4 10-6 10-8 10-10 1000K / T

Melt quenched glass

95(0.6Li2S・0.4SiS2)・5Li4SiO

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SLIDE 13

glass

10

  • 8

10

  • 6

10

  • 4

10

  • 2

100 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4

Conductivity / S cm -1 1000 K / T

Solid-state reaction

σ25 = 3.2 x 10-3 S/cm Ea = 12 kJ/mol

Heating at 360 ℃

Temperature dependence of conductivity for the 70Li2S・30P2S5 glass and glass-ceramic σ25 = 5.4 x 10-5 S/cm Ea = 38 kJ/mol

New superionic metastable crystalline phase

…….. could not be obtained by the usual solid state reaction.

1 0 1 5 2 0 2 5 3 0 3 5 4 0 Intensity (arb.unit) 2 θ / o (C u K α )

as-prepared 360 oC Solid-state reaction

: new phase : thio-LISICON III : Li4P2S6 : Li3PS4

The formation of superionic metastable phase is the most remarkable advantage of glass-based solid electrolytes.

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SLIDE 14

All-solid-state lithium secondary batteries using Li2S-P2S5 glass-ceramics

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SLIDE 15

Stainless steel Insulator Positive electrode

Li2S-P2S5 glass ceramics

Laboratory-scale all-solid-state cell

10mm

Solid electrolyte (SE) Negative electrode

LiCoO2:SE:AB=20:30:3 (wt%) or

In or

SnS-P2S5 glass: SE:AB

All-solid-state batteries（ In / Li2S-P2S5 glass-ceramic / LiCoO2 ） All-solid-state batteries（ In / Li2S-P2S5 glass-ceramic / LiCoO2 ）

Composite electrode is a mixture of three kinds of fine powders

Ionic and electronic conduction paths through SE and conducting additives to active materials

AB

LiCoO2

Solid electrolyte Solid electrolyte Current collector

(S+CuS):SE:AB

Stainless steel

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SLIDE 16

1 2 3 4 5 6 20 40 60 80 100 120 0.1 0.2 0.3 0.4

x in Li1-xCoO2 Cell Voltage / V Capacity / mAh.g-1

64 μA.cm-2

1 5 20, 50 1 5 20, 50

Charge Discharge 25 oC Excellent cycle performance with no loss of capacity up to the cycle number of 500

In / 80Li2S・20P2S5 glass-ceramic / LiCoO2

Cell performance of the all-solid-state battery Cell performance of the all-solid-state battery

The advantage of the glass-ceramics with their high conductivity and dense microstructure would promote smooth charge-discharge reaction in the solid / solid interface between electrolyte and electrode.

50 100 150 200 20 40 60 80 100 120 100 200 300 400 500

Capacity / mAh g-1 Efficiency / % Cycle number

: Charge capacity : Discharge capacity

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SLIDE 17

1 2 3 4 5 6 20 40 60 80 100 120 140 160

Cell Voltage / V Capacity / mAh g

  • 1

100th Cycle 64 μA cm

  • 2

In/LiCoO2 In/LiNi0.5Mn0.5O2 In-Li/a-V2O5 In-Li/Li4/3Ti5/3O4

All-solid-state cell performance using a variety of electrode active materials All-solid-state cell performance using a variety of electrode active materials

In or In-Li / 80Li2S・20P2S5 glass-ceramic / Cathode All-solid-state batteries with high reversibility and high cycle performance

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SLIDE 18

In / 80Li2S-20 P2S5 / LiCoO2 -xCoS NaS2CN(C2H5) 2＋CoCl2 → Co[S2CN(C2H5)2]2 Co[S2CN(C2H5)2]2 → CoS

0.1 wt% coating

  • 800
  • 400

400 800 1200 1600 2000

  • 800
  • 400

Without coating 0.1 wt% coating

after 1st charge after 1st charge before before Z’/Ω Z”/Ω Z”/Ω

I = 10 mA cm-2 (10C)

1 2 3 4 5 6 20 40 60 80 100 120 Cell Voltage / V (vs. In-Li) Capacity / mAh g

  • 1

1st 1st 2nd 2nd 3rd 3rd 1st 1st 2nd 2nd 3rd 3rd

0.1 wt% coating For high rate performance ・Coating on active materials with cobalt sulfide

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SLIDE 19

Preparation of glassy electrode materials for all- solid-state lithium secondary batteries

  • A new concept of all-glass-based battery systems -
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SLIDE 20

Capacity (mAh g-1 of S+Cu)

400 800 1200

64 μA cm-2 0.3 - 2.7 V cutoff

1st 1st 2nd 2nd5th20th 10th 10th 5th20th

200 400 600 800 Capacity (mAh g-1 of CuS) Cell voltage (V) 1 2 3 4 Cell performance of all-solid-state Li / S battery using Cu-S composites prepared by MM as a cathode material In-Li / 80Li2S・20P2S5 glass-ceramic / Cu-S composite Sulfur is utilized as active materials

650 mAhg-1(CuS)

S, CuS composite 3S + Cu MM

Sulfur cathode materials, which could not be used with liquid electrolytes, can be used in all-solid-state batteries using the sulfide glass-ceramic electrolytes. After Machida (2002)

  • Polysulfides formed in the discharge process are soluble in liquid electrolytes.

Theoretical capacity : 1672 mAh g-1 Cheep, Non-toxic Candidate of cathode materials for next- generation secondary batteries

Sulfur

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SLIDE 21

200 400 600 800 1000 1200 1400 2 4 6 8 10 1 2 3 4 5 6

Capacity / mAhg-1 Cell voltage / V Li / Sn

Discharge Charge

1 5 2 10 20 50 5 2 10 20 50 1

Cutoff voltage : 2.0～4.0 V

200 400 600 800 1000 1200 1400 20 40 60 80 100 10 20 30 40 50

Capacity / mAhg-1 Efficiency / % Cycle number Cutoff voltage : 2.0～4.0 V

Discharge Charge

Cell performance using SnS-P2S5 glasses as an anode material 80SnS・20P2S5 glass / 80Li2S・20P2S5 glass-ceramic / LiCoO2 400 mAhg-1 SnS-P2S5 glasses SnS + P2S5 MM Glassy materials contining Sn anode active material Sn0 + Li+ + e- Li4.4Sn

charge discharge

SnS-P2S5 + Li+ + e- Sn0 + Li2S-P2S5

charge Self-formation of high conductive solid electrolytes surrounding the anode active materials

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SLIDE 22

J.L. Souquet et al., Solid State Ionics, 148 (2002) 375. A common network former is used for the electrolyte and electrode materials.

Glassy monolithic cell Glassy monolithic cell

The glassy monolithic cell is expected to facilitate smooth solid-solid contact between electrolyte and electrode, and very promising as a future all-solid-state battery. Li2S-P2S5 glass-ceramic SnS-P2S5 glass Li2S-Cu-S ceramic

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SLIDE 23

Conclusions

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SLIDE 24

CONCLUSIONS CONCLUSIONS CONCLUSIONS CONCLUSIONS

Sulfide glass-based solid electrolytes are suitable to be used

in all-solid-state lithium secondary batteries.

The all-solid-state batteries showed excellent cycle

performance.

In order to obtain high rate performance, electrons and ions

should be smoothly supplied to the active materials through the interface between electrode and electrolyte .

All-solid-state batteries, in which a common sulfide glass

network is used as electrodes and electrolytes, are successfully constructed.

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SLIDE 25

CONCLUSIONS CONCLUSIONS

In order to approach the ultimate goal of all- solid-state lithium secondary battery, the charge transfer at the solid/solid interface between electrolyte and electrode should be analyzed and

  • ptimized to obtain much higher performances.

Thin film battery

Electrode active material

Interface between electrode and electrolyte

Large scale battery

Solid electrolyte