Stabilized solid garnet electrolyte and methods thereof

Patent metadata

Field	Value
Publication number	US-11309581-B2
Application number	US-201916241277-A
Country	US
Kind code	B2
Filing date	Jan 7, 2019
Priority date	Nov 26, 2014
Publication date	Apr 19, 2022
Grant date	Apr 19, 2022

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.

First claim

What is claimed is:

1. A solid garnet electrolyte membrane, comprising:
a bulk composition comprising a lithium garnet chosen from Li 7 La 3 Zr 2 O 12 (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.

2. The solid garnet electrolyte membrane of claim 1 , wherein the lithium garnet is Li 7 La 3 Zr 2 O 12 , and the protonated garnet is Li (7-x) H x La 3 Zr 2 O 12 , wherein x is from 0.1 to 7.

3. The solid garnet electrolyte membrane of claim 1 , wherein the doped LLZO composition comprises Li 7 La 3 Zr 2 O 12 doped with Ga, Nb, or a combination thereof.

4. 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.

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

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

7. The solid garnet electrolyte membrane of claim 1 , wherein the surface composition comprises a surface free of at least one of LiOH, Li 2 CO 3 , or a combination thereof.

8. 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.

9. 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.

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

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

Assignees

• Corning Inc

Inventors

• Badding Michael Edward
• Liu Xinyuan
• Lu Yanxia Ann

Classifications

• C04B2235/5445

  submicron sized, i.e. from 0,1 to 1 micron · CPC title

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title

• C04B2235/3286

  Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate · CPC title

• C04B2235/3251

  Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof · CPC title

• C04B2235/3227

  Lanthanum oxide or oxide-forming salts thereof · CPC title