# US 11,309,581 B2 · Stabilized solid garnet electrolyte and methods thereof

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- Number: US 11,309,581 B2
- Document ID: US11309581B2
- Status: Granted
- Kind: B2
- Application number: 16/241,277
- Filed: 2019-01-07
- Published: 2019-05-16
- Granted: 2022-04-19
- Earliest claimed: 2014-11-26
- Assignees: Corning Incorporated
- Applicants: Corning Incorporated
- Inventors: Michael Edward Badding; Xinyuan Liu; Yanxia Ann Lu
- Web page: https://patentgrep.com/patent/US11309581B2

## CPC

- H01M 10/0562: Solid materials
- C04B 35/486: Fine ceramics
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/405: {Alloys based on lithium}
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 4/9016: {Oxides, hydroxides or oxygenated metallic salts}
- H01M 8/08: Fuel cells with aqueous electrolytes
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 12/08: composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
- C04B 2235/3203: Lithium oxide or oxide-forming salts thereof
- C04B 2235/3227: Lanthanum oxide or oxide-forming salts thereof
- C04B 2235/3251: Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
- C04B 2235/3286: Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
- C04B 2235/5436: micrometer sized, i.e. from 1 to 100 micron
- C04B 2235/5445: submicron sized, i.e. from 0,1 to 1 micron
- C04B 2235/5472: Bimodal, multi-modal or multi-fraction
- C04B 2235/5481: Monomodal
- C04B 2235/764: Garnet structure A3B2(CO4)3
- H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
- H01M 2300/0002: Aqueous electrolytes
- H01M 2300/0071: Oxides
- Y02E 60/10: Energy storage using batteries
- Y02E 60/50: Fuel cells
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

An air stable solid garnet composition, comprising: a bulk composition and a surface protonated composition on at least a portion of the bulk composition as defined herein, and the protonated surface composition is present on at least a portion of the exterior surface of the bulk composition at a thickness of from 0.1 to 10,000 nm. Also disclosed is a composite electrolyte structure, and methods of making and using the composition and the composite electrolyte structure.

## Claims

### Claim 1

A solid garnet electrolyte membrane, comprising:
a bulk composition comprising a lithium garnet chosen from Li7La3Zr2O12 (LLZO) and doped LLZO compositions; and
a surface composition comprising a protonated garnet on at least a portion of the exterior surface of the lithium garnet,
wherein:
the surface protonated portion of the garnet is compositionally stable in air and insensitive to carbon dioxide, and
the protonated garnet on at least a portion of the exterior surface of the lithium garnet comprises a layer having a thickness of from 0.1 to 100 nm.

### Claim 2 (depends on 1)

The solid garnet electrolyte membrane of claim 1, wherein the lithium garnet is Li7La3Zr2O12, and the protonated garnet is Li(7-x)HxLa3Zr2O12, wherein x is from 0.1 to 7.

### Claim 3 (depends on 1)

The solid garnet electrolyte membrane of claim 1, wherein the doped LLZO composition comprises Li7La3Zr2O12 doped with Ga, Nb, or a combination thereof.

### Claim 4 (depends on 1)

The solid garnet electrolyte membrane of claim 1, wherein the protonated garnet on at least a portion of the exterior surface of the lithium garnet comprises the entire exterior surface of the lithium garnet.

### Claim 5 (depends on 1)

The solid garnet electrolyte membrane of claim 1, wherein the surface composition has a lithium concentration of from 0.1 to 46 mol %.

### Claim 6 (depends on 1)

The solid garnet electrolyte membrane of claim 1, wherein the surface composition is substantially free of an electrically insulating Li surface species.

### Claim 7 (depends on 1)

The solid garnet electrolyte membrane of claim 1, wherein the surface composition comprises a surface free of at least one of LiOH, Li2CO3, or a combination thereof.

### Claim 8 (depends on 1)

A composite electrolyte structure comprising:
a protected anode structure comprising:
a first layer comprising a ceramic electrolyte comprising the solid garnet electrolyte membrane of claim 1;
a second layer comprising a source of lithium metal, wherein the first layer and the second layer are in physical contact; and
a cathode.

### Claim 9 (depends on 8)

The composite electrolyte structure of claim 8, further comprising an aqueous catholyte positioned between and in contact with the protected anode structure and the cathode.

### Claim 10 (depends on 8)

The composite electrolyte structure of claim 8, wherein the cathode is a lithium cobalt oxide compound.

### Claim 11 (depends on 1)

An energy storage device comprising a cathode, an anode, and the solid garnet electrolyte membrane of claim 1.