Electrolyte material and methods of forming

Patent metadata

Field	Value
Publication number	US-11522217-B2
Application number	US-202117230625-A
Country	US
Kind code	B2
Filing date	Apr 14, 2021
Priority date	Apr 14, 2020
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

A solid electrolyte material can include an ammonium-containing complex metal halide. In an embodiment, the ammonium-containing complex metal halide can be represented by (NH 4 ) n M 3-z (Me k+ ) f X n+3-z+k*f , wherein 0<n, 0≤z<3, 2≤k<6, 0≤f≤1; M comprises at least an alkali metal element, X comprises a halogen, and Me comprises a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element or any combination thereof.

First claim

What is claimed is:

1. A solid electrolyte material, comprising a material including an ammonium-containing complex metal halide represented by (NH 4 ) n M 3-z (Me k+ ) f X n+3-z +k*f , wherein 0<n, 0≤z<3, 2≤k<6, 0≤f≤1; M comprises an alkali metal element, X comprises a halogen, and Me comprises a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element or any combination thereof.

2. The solid electrolyte material of claim 1 , wherein the ammonium-containing complex metal halide is constituted of A t and Bu (1-t) , wherein t≥0.01 and t≥0.2, and wherein A comprises ammonium and B is free of ammonium.

3. The solid electrolyte material of claim 2 , wherein A is represented by (NH 4 ) n Li 3-z (Me k+ ) f X 3-z+k*f+n , and B is represented by (Li 1-d-e Na d M e ) 2 Li 1-z′ (Me′ k+ ) f′ X 3-z′+k*f , wherein:
Me and Me′ independently includes a rare earth element, Zr, a divalent metal element, a trivalent metal element other the rare earth, a tetravalent metal element other than Zr, a pentavalent element, a hexavalent element or any combination thereof;
M is K, Rb, Cs, or any combination thereof;
2≤ k≤ 6;

0≤ d≤ 1;

0≤ e< 1;

−1≤ z′≤ 1;

0≤ f≤ 1;

0< f′≤ 1;
0< n;
0≤ z≤ 3;

n=0.33, 0.5 or 1 or 1.5 or 2 or 3 or 4 when z=3; and
X includes at least one halogen and optionally at least one of —NH 2 or —OH, or —BH 4 or —BF 4 .

4. The solid electrolyte material of claim 1 , wherein Me comprises one or more of a rare earth element, alkaline earth metal element a 3d transition-metal, Zn, Ga, Al, Ge, Zr, Hf, Ti, Sn, Th, Ta, Nb, Mo, W, Sb, In, Bi or any combination thereof.

5. The solid electrolyte material of claim 4 , wherein M comprises at least one of Li and Na.

6. The solid electrolyte material of claim 2 , wherein Me consists of at least one of La, Ce, Gd, Er, Yb, Sc, and Y.

7. The solid electrolyte material of claim 6 , wherein the material is represented by (NH 4 ) n Li 3-z (Me k+ ) f X 3-z+k*f+n .

8. The solid electrolyte material of claim 1 , wherein the complex ammonium-containing metal halide is represented by (NH 4 ) n (Li (1-d-e) Na (d) M′ (e) ) 2 Li (1-z) Me 3+ (1-u-p-q-r) Me 4+ (u) Me 2+ (p) Me 5+ (q) Me 6+ (r) (Cl (1-y-w) Br (y) I (w) ) (6+u-p+2q+3r-z+n) ,
0< n;
−1≤ z< 1;

0≤ d< 1;

0≤ e< 1;

M 3+ includes a rare-earth element, In, Bi, Ga, Al, Sb, Sn or any combination thereof;
M′ is K, Rb, Cs, or any combination thereof;
Me 4+ is Zr 4+ , Hf 4+ , Ti 4+ , Sn 4+ , Th 4+ , Ge 4+ or any combination thereof;
Me 2+ is Mg 2+ , Zn 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Yb 2+ , Eu 2+ or any combination thereof;
Me 5+ is Ta 5+ , Nb 5+ , W 5+ , Sb 5+ , or any combination thereof;
Me 6+ is W 6+ , Me 6+ , or any combination thereof;
0<= w<= 1;
0<= y<= 1;
0<= u< 0.95;
0<= p< 0.95;
0<= q< 0.95;
0<= r< 0.95.

9. The solid electrolyte material of claim 2 , wherein A is represented by (NH 4 )(Me k+ ) f X k*f+n , and B is represented by M 2 Li(Me k+ ) f X 3+k*f , wherein M comprises at least one alkali metal element, Me comprises at least one element selected from the group consisting of rare earth element and Zr, n=0.33 or 0.5 or 1 or 1.5 or 2 or 3 or 4, and X includes at least one halogen.

10. The solid electrolyte material claim 2 , wherein A is represented by (NH 4 ) 3 Li 3 YX 9 , and B is represented by (Li 1-d Na d ) 2 LiREX 6 , wherein RE comprises at least one rare earth element, 0≤d<1, and X includes at least one halogen.

11. The solid electrolyte material claim 10 , wherein X consists of at least one of F, Cl, Br, and I, and optionally, at least one of —NH 2 (amide), —(NH) 0.5 (imide), —OH (hydroxide), —BH 4 and —BF 4 groups.

12. The solid electrolyte material of claim 2 , wherein A is represented by (NH 4 ) n YX 3+n , n=0.5, 1, 2, or 3 and B is represented by M 2 LiREX 6 , wherein M is Li or Li and Na or Li and Cs, RE comprises at least one rare earth element, and X includes at least one halogen.

13. The solid electrolyte material of claim 1 , wherein the ammonium-containing complex metal halide comprises a single phase or a plurality of phases.

14. The solid electrolyte material of claim 2 , comprising a first phase including ammonium and a second phase including B.

15. The solid electrolyte material of claim 2 , wherein the first phase comprises A and is free of B.

16. The solid electrolyte material of claim 14 , wherein the second phase consists of B.

17. The solid electrolyte material of claim 14 , further comprising a third phase including ammonium, wherein the first phase and the third phase constitute A.

18. The solid electrolyte material of claim 14 , wherein the second phase comprises Li 3 REX 6 , wherein RE comprises a rare earth element, Zr, or a combination thereof and X consist of one or more halogen and optionally an anion group.

19. The solid electrolyte material of claim 14 , wherein the first phase comprises (NH 4 ) 3 Li 3 Me k+ X 6+k or (NH 4 )Me k+ X 3+k wherein Me comprises a rare earth element, Zr, or a combination thereof, and X consists of one or more halogen and optionally an anion group.

20. The solid electrolyte material of claim 17 , wherein the first phase comprises (NH 4 ) 3 Li 3 RE k+ X 6+k and the third phase comprises (NH 4 ) 3 RE k+ X 3+k , wherein RE comprises a rue earth element, Zr, or a combination thereof, and X consist of one or more halogen and optionally anion group.

Assignees

• Saint Gobain Ceramics

Inventors

• Ouspenski Vladimir
• Assat Gaurav

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0525

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

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/008

  Halides · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title