Methods for growth of lithium-rich antiperovskite electrolyte films and use thereof
View Patent ↗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 Li 3 OCl from a target largely composed of Li 2 O and LiCl. Exposure of the target to a pulsed laser beam deposits antiperovskite electrolyte Li 3 OCl 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).
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.