Stabilized solid garnet electrolyte and methods thereof

Patent metadata

Field	Value
Publication number	US-10211481-B2
Application number	US-201514934297-A
Country	US
Kind code	B2
Filing date	Nov 6, 2015
Priority date	Nov 26, 2014
Publication date	Feb 19, 2019
Grant date	Feb 19, 2019

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:

1. A solid garnet electrolyte membrane, comprising:
a bulk composition comprising a Li (7-z) La (3-y) Ga y Zr (2-z) Nb z O 12 lithium garnet; and
a surface composition comprising a Li (7-z-x) H x La (3-y) Ga y Zr (2-z) Nb z O 12 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 wherein x is from 0.1 to 7, y is from 0.1 to 0.3, and z is from 0.1 to 0.3.

2. The solid garnet electrolyte membrane of claim 1 wherein
the lithium garnet is Li 6.75 La 2.9 Ga 0.1 Nb 0.25 Zr 1.75 O 12 and
the protonated garnet is Li (6.75-x) H x La 2.9 Ga 0.1 Nb 0.25 Zr 1.75 O 12 ,

where x is from 0.1 to 6.75.

3. 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.

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 a layer having a thickness of from 0.1 to 100 nm.

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 situated 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. A method of making the solid garnet composition of claim 1 , comprising:
contacting an air sensitive lithium containing garnet with a protic acid to form the solid garnet composition having a protonated garnet surface composition.

12. The method of claim 11 wherein the protic acid is selected from at least one of: a mineral acid an organic acid or a combination thereof.

13. The method of claim 11 further comprising contacting the air stable and carbon dioxide insensitive solid garnet composition having the protonated garnet surface with a source of lithium ions to regenerate the air sensitive lithium containing solid garnet.

14. The method of claim 13 wherein the contacting with a source of lithium ions is accomplished in a sealed cell structure.

15. The method of claim 13 wherein the source of lithium ions is lithium metal.

16. The solid garnet electrolyte membrane of claim 1 , wherein the membrane is sintered.

17. An energy storage device comprising the solid garnet electrolyte membrane of claim 1 .

18. An energy storage device comprising the composite electrolyte structure of claim 8 .

Assignees

• Corning Inc

Inventors

• Badding Michael Edward
• Liu Xinyuan
• Lu Yanxia Ann

Classifications

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title

• H01M10/0585

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/9016

  Oxides, hydroxides or oxygenated metallic salts · CPC title

• C04B2235/5445

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