# US 10,483,585 B2 · Ion-conducting glass ceramic having garnet-like crystal structure

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- Number: US 10,483,585 B2
- Document ID: US10483585B2
- Status: Granted
- Kind: B2
- Application number: 15/215,421
- Filed: 2016-07-20
- Published: 2016-11-10
- Granted: 2019-11-19
- Earliest claimed: 2014-01-22
- Assignees: Schott AG
- Applicants: Schott AG
- Inventors: Meike Schneider; Oliver Hochrein; Wolfgang Schmidbauer; Miriam Kunze
- Web page: https://patentgrep.com/patent/US10483585B2

## CPC

- C03B 5/021: {by induction heating}
- C03C 3/12: Silica-free oxide glass compositions
- C03C 3/125: {containing aluminium as glass former}
- C03C 4/18: for ion-sensitive glass
- C03C 10/00: Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C 21/002: {to perform ion-exchange between alkali ions (C03C21/005 takes precedence)}
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0562: Solid materials
- C03C 2204/00: Glasses, glazes or enamels with special properties
- H01M 2300/002: Inorganic electrolyte
- H01M 2300/0071: Oxides
- H01M 2300/0074: Ion conductive at high temperature
- H01M 2300/0077: based on zirconium oxide
- Y02E 60/10: Energy storage using batteries
- C03B: MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A glass ceramic containing lithium-ions and having a garnet-like main crystal phase having an amorphous proportion of at least 5% is disclosed. The garnet-like main crystal phase preferably has the chemical formula Li7+x−yMxIIM3−xIIIM2−yIVMyVO12, wherein MII is a bivalent cation, MIII is a trivalent cation, MIV is a tetravalent cation, MV is a pentavalent cation. The glass ceramic is prepared by a melting technology preferably within a Skull crucible and has an ion conductivity of at least 5·10−5 S/cm, preferably of at least 1·10−4 S/cm.

## Claims

### Claim 1

A lithium-ion conducting glass ceramic comprising a garnet-like main crystal phase having an amorphous proportion of at least 5 wt.-%, wherein said garnet-like main crystal phase has the chemical formula:
Li7+x−yMxIIM3−xIIIM2−yIVMyVO12,
wherein MII is a bivalent cation, MIII a trivalent cation, MIv a tetravalent cation, and MV a pentavalent cation.

### Claim 2 (depends on 1)

The glass ceramic of claim 1, wherein 0≤x<3 and 0≤y<2.

### Claim 3 (depends on 1)

The glass ceramic of claim 1, wherein said glass ceramic is ceramicised from a starting glass comprising 10-25 wt.-% of Li2O.

### Claim 4 (depends on 1)

The glass ceramic of claim 1, comprising in total 40-60 wt.-% of an oxide of at least one lanthanoid.

### Claim 5 (depends on 1)

The glass ceramic of claim 1, wherein said glass ceramic comprises in total 40-60 wt.-% of an oxide of at least one lanthanoid and is ceramicised from a starting glass comprising 10-25 wt.-% of Li2O.

### Claim 6 (depends on 1)

The glass ceramic of claim 1, wherein 0≤x≤2 and 0≤y≤1.

### Claim 7 (depends on 1)

The glass ceramic of claim 1, wherein said amorphous proportion is a maximum of 40 wt.-%.

### Claim 8 (depends on 1)

The glass ceramic of claim 1, having an ion-conductivity of at least 5·10−5 S/cm.

### Claim 9 (depends on 1)

The glass ceramic of claim 1, wherein said glass ceramic is ceramicised from a starting glass comprising in total 40-60 wt.-% of La2O3.

### Claim 10 (depends on 1)

The glass ceramic of claim 1, wherein said glass ceramic is ceramicised from a starting glass comprising 15-35 wt.-% of ZrO2.

### Claim 11 (depends on 1)

The glass ceramic of claim 1, wherein said glass ceramic is ceramicised from a starting glass comprising 1-5 wt.-% of one oxide being selected from the group consisting of Al2O3, Bi2O3, Ga2O3, Y2O3, Fe2O3, Cr2O3, In2O3, and mixtures thereof.

### Claim 12 (depends on 11)

The glass ceramic of claim 11, wherein said glass ceramic is ceramicised from a starting glass comprising 1-5 wt.-% of one oxide being selected from the group consisting of Al2O3, Bi2O3, Ga2O3, Y2O3, Fe2O3, Cr2O3, In2O3, and mixtures thereof.

### Claim 13 (depends on 1)

The glass ceramic of claim 1, wherein said glass ceramic is ceramicised from a starting glass comprising 1-20 wt.-% of an oxide being selected from the group consisting of Ta2O5, Nb2O5, V2O5, P2O5, and mixtures thereof.

### Claim 14 (depends on 1)

The glass ceramic of claim 1, wherein said glass ceramic is ceramicised from a starting glass comprising 1-5 wt.-% of an oxide being selected from the group consisting of TiO2, HfO2, SnO2, and mixtures thereof.

### Claim 15 (depends on 1)

The glass ceramic of claim 1, wherein said glass ceramic is ceramicised from a starting glass comprising 1-10 wt.-% of at least of an oxide being selected from the group consisting of RO, ZnO, and mixtures thereof, wherein R is an alkaline earth ion.

### Claim 16 (depends on 1)

A battery comprising a glass ceramic according to claim 1, wherein said battery is configured as a battery selected from the group consisting of a lithium-ion battery, an all-solid-state battery, a lithium-air battery, and a lithium-sulfur battery.

### Claim 17 (depends on 16)

The battery of claim 16, wherein said glass ceramic is configured as an electrolyte, as an electrolyte additive or as a component of a composite electrolyte.

### Claim 18

A lithium-ion conducting glass ceramic comprising:
a garnet-like main crystal phase having an amorphous proportion of greater than 10 wt.-% and less than 40 wt.-%,
wherein said garnet-like main crystal phase has the chemical formula:
Li7+x−yMxIIM3−xIIIM2−yIVMyVO12,
wherein 0≤x<3 and 0≤y<2,
wherein M is selected from the group consisting of La, Zr, Al, Ta, and Nb, and
wherein MII is a bivalent cation, MIII a trivalent cation, MIV a tetravalent cation, and MV a pentavalent cation.

### Claim 19 (depends on 18)

The glass ceramic of claim 18, wherein 0≤x≤2 and 0≤y≤1.

### Claim 20 (depends on 18)

The glass ceramic of claim 18, comprising in total 40-60 wt.-% of an oxide of at least one lanthanoid.

### Claim 21 (depends on 18)

The glass ceramic of claim 18, wherein said amorphous proportion is a maximum of 40 wt.-%.

### Claim 22 (depends on 18)

The glass ceramic of claim 18, having an ion-conductivity of at least 5·10−5 S/cm.

### Claim 23 (depends on 18)

The glass ceramic of claim 18, having an ion-conductivity of at least 1·10−4 S/cm.

### Claim 24 (depends on 18)

The glass ceramic of claim 18, wherein the amorphous proportion is smaller than or equal to 30 wt.-%.