Methods for growth of lithium-rich antiperovskite electrolyte films and use thereof

Patent metadata

Field	Value
Publication number	US-10044061-B2
Application number	US-201514736109-A
Country	US
Kind code	B2
Filing date	Jun 10, 2015
Priority date	Jun 11, 2014
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

A process for preparing a lithium-rich antiperovskite electrolyte film involves forming a composite target of precursor metal oxide(s) and metal halide(s), and exposing the target to a pulsed laser beam under conditions suitable for depositing a film of lithium-rich antiperovskite on a surface. In some embodiments the process is used to prepare a film of Li3OCl from a target largely composed of Li2O and LiCl. Exposure of the target to a pulsed laser beam deposits antiperovskite electrolyte Li3OCl on a substrate. In another embodiment, sputtering may be used to prepare films of lithium-rich antiperovskites using the composite target of precursor metal oxide(s) and metal halide(s).

First claim

What is claimed is:

1. A process comprising:
preparing a film of an antiperovskite material on a surface by
providing a target comprising a mixture of precursors, the mixture having a ratio of atoms present in the precursors chosen to provide a desired ratio of atoms present in an antiperovskite material; and
exposing the target thereafter to a pulsed laser beam under conditions suitable for deposition of atoms present in the target onto a surface to form the antiperovskite material.

2. The process of claim 1 , wherein providing the target comprises:
compressing the mixture of precursors into a pressed object; and
annealing the pressed object under temperature and time conditions that do not convert more than 10 wt % of the mixture of precursors into the antiperovskite material prior to exposing the target to the pulsed laser beam.

3. The process of claim 2 , wherein the antiperovskite material has the formula Li 3 OX z Y (1-z) , wherein X and Y are halogens, and wherein 0≤z≤1.

4. The process of claim 3 , wherein 0.1≤z≤0.8.

5. The process of claim 3 , wherein 0≤z<0.10.

6. The process of claim 2 , wherein the antiperovskite material has the formula Li (3-x) M x/2 OA, wherein:
0≤x≤3;
M is an alkaline earth metal; and
A is a halide or a combination of halides.

7. The process of claim 6 , wherein the alkaline earth metal is Mg 2+ , Ca 2+ , Ba 2+ , Sr 2+ , or a combination thereof.

8. The process of claim 6 , wherein the halide anions are fluoride, chloride, bromide, iodide or a combination thereof.

9. The process of claim 6 , wherein 0.1≤x≤0.8.

10. The process of claim 6 , wherein 0≤x<0.10.

11. The process of claim 2 , wherein the antiperovskite material has the formula Li (3-x) Q (x/3) OA wherein 0.1≤x≤3, wherein Q is a trivalent metal, and wherein A is one or more halide anions.

12. The process of claim 11 , wherein Q is aluminum.

13. The process of claim 11 , wherein the halide anions are fluoride, chloride, bromide, iodide, or a combination thereof.

14. The process of claim 11 , wherein 0.1≤x≤0.8.

15. The process of claim 11 , wherein 0≤x<0.10.

16. A process comprising:
preparing a film of Li 3 OCl by the steps of
forming a target comprising at least 90 wt % of a mixture of Li 2 O and LiCl, the mixture having a molar ratio of Li 2 O:LiCl within a range of 0.9:1.1 to 1.1:0.9; and
exposing the target thereafter to a pulsed laser beam under conditions suitable for depositing a film comprising Li 3 OCl on a surface.

17. The process of claim 16 , wherein the step of forming the target comprises:
forming a powder mixture of Li 2 O and LiCl, the powder mixture having a molar ratio of Li 2 O:LiCl within a range of 0.9:1.1 to 1.1:0.9;
pressing the powder mixture into a disk having a structure; and
annealing the disk under conditions suitable for physically stabilizing the disk without converting more than 10 wt % of the powder mixture into Li 3 OCl prior to exposing the target to the pulsed laser beam.

18. A process for preparing a multilayered article comprising:
depositing a first layer of metal on a substrate;
exposing a target comprising a mixture of Li 2 O and LiCl, the mixture having a molar ratio of Li 2 O:LiCl within a range of 0.9:1.1 to 1.1:0.9, to a pulsed laser beam under conditions suitable for depositing a film comprising antiperovskite Li 3 OCl on the first layer of metal;
depositing a second layer of metal on the film comprising antiperovskite Li 3 OCl; and
depositing a protective layer on the second layer of metal.

19. The process of claim 18 , further comprising forming a target consisting essentially of the mixture of Li 2 O and LiCl before exposing the target to the pulsed laser beam.

20. The process of claim 19 , wherein forming the target comprises:
forming a powder mixture of Li 2 O and LiCl;
pressing the powder mixture into a disk; and
annealing the disk under conditions suitable for fusing the powders together to form the target without converting more than 10 wt % of the mixture of precursors into the antiperovskite material prior to exposing the target to the pulsed laser beam.

Assignees

• Los Alamos Nat Security Llc
• Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The Univ Of Nevada Las Vegas

Inventors

• Lu Xujie
• Howard John
• Daemen Luc
• Zhao Yusheng
• Jia Quanxi

Classifications

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title

• C04B2235/3208

  Calcium oxide or oxide-forming salts thereof, e.g. lime · CPC title

• C23C14/28

  by wave energy or particle radiation (C23C14/32 - C23C14/48 take precedence) · CPC title

• H01M10/0525

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

• C04B2235/3215

  Barium oxides or oxide-forming salts thereof · CPC title