Electrolyte material and methods of forming

Patent metadata

Field	Value
Publication number	US-2021320326-A1
Application number	US-202117230625-A
Country	US
Kind code	A1
Filing date	Apr 14, 2021
Priority date	Apr 14, 2020
Publication date	Oct 14, 2021
Grant date	—

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 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 M comprises Li.

3 . The solid electrolyte material of claim 1 , wherein M consists of Li and at least one of Na, K, Cs, and Rb.

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 1 , 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.

6 . The solid electrolyte material of claim 1 , wherein the material 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;
0≤ d< 1;

0≤ e< 1;

( d+e )<1;
−1<= z<= 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<=( y+w )<=1;
0<= u< 0.95;
0<= p< 0.95;
0<= q< 0.95;
0<= r< 0.95; and
0<=( u+p+q+r )<=1.

7 . The solid electrolyte material of claim 1 , wherein Me consists of at least one of La, Ce, Gd, Er, Yb, Sc, and Y.

8 . The solid electrolyte material of claim 1 , wherein the material is represented by (NH 4 ) n Li 3-z (Me k+ ) f X 3-z+k*f+n .

9 . A solid electrolyte material, comprising an ammonium-containing complex metal halide, wherein the metal comprises at least one alkali metal element, and wherein the complex metal halide exhibits ionic conductivity in bulk.

10 . The solid electrolyte material of claim 9 , wherein the ammonium-containing complex metal halide comprises a single phase or a plurality of phases.

11 . The solid electrolyte material of claim 9 , wherein the ammonium-containing complex 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;

( d+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+ , Mo 6+ , or any combination thereof;
0<= w<= 1;
0<= y<= 1;
0<=( y+w )<=1;
0<= u< 0.95;
0<= p< 0.95;
0<= q< 0.95;
0<= r< 0.95;
0<=( u+p+q+r )<=1.

12 . The solid electrolyte material of claim 9 , wherein the ammonium-containing complex metal halide is 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 one 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.

13 . The solid electrolyte material of claim 9 , wherein the ammonium-containing complex metal halide is represented by (NH 4 ) n Li 3-z (Me k+ ) f X 3-z+k*f+n .

14 . A solid electrolyte material, comprising an ammonium-containing complex metal halide constituted of A t and B (1-t) , wherein 10 −6 <t≤1, and A comprises ammonium and B is free of ammonium, and wherein the metal comprises at least one alkali metal element.

15 . The solid electrolyte material of claim 14 , 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;

0<=( d+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 a halogen.

16 . The solid electrolyte material of claim 14 , 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 and optionally at least one of —NH 2 or —OH, or —BH 4 or —BF 4 .

17 . The solid electrolyte material of claim 16 , wherein RE consists of at least one of La, Ce, Gd, Er, Yb, Sc, and Y.

18 . The solid electrolyte material of claim 14 , wherein A is represented by (NH 4 ) n YX 3+n , n=0.5, 1, 2, 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.

19 . The solid electrolyte material of claim 14 , wherein t≥0.01 and t≤0.2.

20 . A solid state lithium battery, comprising a layer comprising the solid electrolyte material of claim 14 , wherein the layer comprises an electrolyte layer, a mixed ion and electron conductive layer, or a combination thereof.

Assignees

• Saint Gobain Ceramics

Inventors

• Ouspenski Vladimir
• Assat Gaurav

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01B1/06

  mainly consisting of other non-metallic substances · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M2300/008

  Halides · CPC title