Annealed garnet electrolyte separators

Patent metadata

Field	Value
Publication number	US-2017214084-A1
Application number	US-201615007908-A
Country	US
Kind code	A1
Filing date	Jan 27, 2016
Priority date	Jan 27, 2016
Publication date	Jul 27, 2017
Grant date	—

Abstract

Set forth herein are pellets, thin films, and monoliths of lithium-stuffed garnet electrolytes having engineered surfaces. These engineered surfaces have a list of advantageous properties including, but not limited to, low surface area resistance, high Li + ion conductivity, low tendency for lithium dendrites to form within or thereupon when the electrolytes are used in an electrochemical cell. Other advantages include voltage stability and long cycle life when used in electrochemical cells as a separator or a membrane between the positive and negative electrodes. Also set forth herein are methods of making these electrolytes including, but not limited to, methods of annealing these electrolytes under controlled atmosphere conditions. Set forth herein, additionally, are methods of using these electrolytes in electrochemical cells and devices. The instant disclosure further includes electrochemical cells which incorporate the lithium-stuffed garnet electrolytes set forth herein.

First claim

What is claimed is:

1 . A thin electrolyte separator,
having top and bottom surfaces and a thickness therebetween,
wherein the top or bottom surface length or width is greater than the thickness by a factor of ten (10) or more, and the thickness is from about 10 nm to about 100 μm;
wherein the electrolyte bulk is characterized by the chemical formula Li x La 3 Zr 2 O 12 y(Al 2 O 3 ), wherein 3≦x≦8 and 0≦y≦1; wherein either the top or bottom surface is characterized as having a layer thereupon, greater than 1 nm and less than 1 μm, comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.

2 . A thin electrolyte separator,
having top and bottom surfaces and a thickness therebetween,
wherein the top or bottom surface length or width is greater than the thickness by a factor of ten (10) or more, and the thickness is from about 10 nm to about 100 μm;
wherein the electrolyte bulk is characterized by the chemical formula Li x La 3 Zr 2 O 12 y(Al 2 O 3 ), wherein 3≦x≦8 and 0≦y≦1; wherein either the top or bottom surface is characterized as having substantially no layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.

3 . The electrolyte separator of claim 1 or 2 , wherein the top or bottom surface length or width is from about 100 μm to 100 cm.

4 . The electrolyte separator of claim 1 or 2 , wherein x is 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or 8.

5 . The electrolyte separator of claim 1 or 2 , wherein the electrolyte bulk is characterized by the chemical formula Li 3 La 3 Zr 2 O h 0.2(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.25 (Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.3(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.35(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.4(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.45(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.65(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.7(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.75(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.9 (Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.95(Al 2 O 3 ), Li 3 La 3 Zr 2 O h (Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.2(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.25(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.3 (Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.35(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.4(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.45(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.7(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.75(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.9(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.95(Al 2 O 3 ), Li 5 La 3 Zr 2 O h (Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.2(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.25(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.3(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.35(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.4(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.45(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.7(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.75(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.9(Al 2 O 3 ), Li 6 La 3 Zr 2 O h 0.95(Al 2 O 3 ), Li 6 La 3 Zr 2 O h (Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.2(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.25(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.3(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.35(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.4(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.45(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.65(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.7(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.75(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.9(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.95(Al 2 O 3 ), or Li 7 La 3 Zr 2 O h (Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.3 (Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.35(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.4(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.45(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.65(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.7(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.75(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.9(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.95(Al 2 O 3 ), Li 7 La 3 Zr 2 O h (Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.2(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.25(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.3 (Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.35(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.4(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.45(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.65(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.9(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.95(Al 2 O 3 ), or Li 8 La 3 Zr 2 O h (Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.3(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.35(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.4(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.45(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.65(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.9(Al 2 O 3 ), Li 8 La 3 Zr 2 O h 0.95(Al 2 O 3 ), or Li 8 La 3 Zr 2 O h (Al 2 O 3 );
wherein subscript h is a rational number from 0 to 15 and is selected to maintain charge neutrality.

6 . The electrolyte separator of any one of claim 1 - 5 , wherein the electrolyte bulk is characterized by a chemical formula different from the top or bottom surface of the electrolyte separator.

7 . The electrolyte separator of any one of claim 1 - 6 ,
wherein the electrolyte bulk is characterized by the chemical formula Li x1 La 3 Zr 2 O 12 y(Al 2 O 3 ), wherein 3≦x1≦8 and 0≦y≦1; wherein the top or bottom surface or both is/are characterized by the chemical formula Li x2 La 3 Zr 2 O 12 y(Al 2 O 3 ), wherein 3≦x1≦8 and 0≦y≦1; wherein x2 is less than x1.

8 . The electrolyte separator of any one of claim 1 and 3 - 7 , wherein either the top or bottom surface is characterized as having less than a 0.5 μm thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.

9 . The electrolyte separator of claim 8 , wherein either the top or bottom surface is characterized as having less than a 0.35 μm thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.

10 . The electrolyte separator of claim 9 , wherein either the top or bottom surface is characterized as having less than a 0.25 μm thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.

11 . The electrolyte separator of claim 10 , wherein either the top or bottom surface is characterized as having less than a 0.15 μm thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.

12 . The electrolyte separator of claim 11 , wherein

Assignees

• Quantumscape Corp

Inventors

• Cheng Lei
• Iyer Sriram
• GARDNER Will
• Holme Tim
• Li Shuang
• Chao Cheng-Chieh
• Donnelly Niall
• Allenic Arnold

Classifications

• C04B2235/6025

  Tape casting, e.g. with a doctor blade · CPC title

• H01M10/056

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• C04B35/62218

  obtaining ceramic films, e.g. by using temporary supports · CPC title

• H01M10/058

  Construction or manufacture · CPC title

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title