Electrolyte material and methods of forming

Patent metadata

Field	Value
Publication number	US-12308384-B2
Application number	US-202318361479-A
Country	US
Kind code	B2
Filing date	Jul 28, 2023
Priority date	May 17, 2021
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

A solid electrolyte material can include a halide material represented by Li 3−x−f M f RE 1−y Me k y (Cl 1−u−p−q Br u F p I q ) 6−x+y*(k−3) , wherein the halide material includes at least two halide anions. The halide material can include reduced content of one or more impurity phase, including binary halide phase, oxyhalide phase, or ternary halide phase.

First claim

What is claimed is:

1. A solid electrolyte material, comprising a halide material represented by Li a M a′ Me b Me′ b ′X c X′ c′ ,
wherein:
M is at least one alkali metal element other than Li;
Me is different from M and includes a rare earth element;
Me′ is different from M and Me and includes a divalent element, tetravalent element, a trivalent element, or a combination thereof; and
X is a halogen;
X′ is a halogen other than X;
(a+a′) >0;
(b+b′) >0; and
c≥c′; and

wherein the halide material comprises a total content of a water insoluble impurity phase of less than 0.11 wt % and a total content of at least 0.0001 wt % and not greater than 9 wt % of binary halide phase for a total weight of the halide material, wherein the binary halide phase comprises lithium halide, rare-earth halide, or a combination thereof.

2. The solid electrolyte material of claim 1 , wherein the halide material has a crystallography phase transition when c/(c+c′) is in the stoichiometry range from (c/(c+c′))*0.84 to (c/(c+c′)) t *1.16, wherein (c/(c+c′)) t corresponds to a crystallography phase transition boundary on the crystallography phase diagram at the temperature from 20° C. to 25° C.

3. The solid electrolyte material of claim 1 , wherein the halide material has a crystallography phase transition when b/(b+b′) is in the stoichiometry range from (b/(b+b′ *0.84 to (b/(b+b′)) t *1.16, wherein (b/(b+b′)) t corresponds to a crystallography phase transition boundary on the crystallography phase diagram at a temperature from 20° C. to 25° C.

4. The solid electrolyte material of claim 1 , wherein the halide material has a crystallography phase transition when a/(a+a′) is in the stoichiometry range from (a/(a+a′)) t * 0.84 to (a/(a+a′)) t *1.16, wherein (a/(a+a′)) t corresponds to a crystallography phase transition boundary on the crystallography phase diagram at the temperature from 20° C. to 25° C.

5. The solid electrolyte material of claim 1 , wherein the halide material comprises a total content of an oxyhalide phase of not greater than 7 wt % and a total content of a ternary halide phase of not greater than 7 wt %.

6. The solid electrolyte material of claim 1 , wherein the total content of the binary halide phase is not greater than 2 wt % for the total weight of the halide material.

7. The solid electrolyte material of claim 6 , wherein halide material is represented by Li a−f M a′ RE b Me′ k b′ (Cl c Br c′ ) 6−f+(k−3)*b′ , wherein (a+a′)=3, −1≤f≤1, (c+c′)=1, and (b+b′)=1, c>c′>0, and 0.63≤c/(c+c′)≤0.98.

8. The solid electrolyte material of claim 6 , wherein the halide material is represented by Li 3−f RE b Me′ k b′ (Cl c Br c′ ) 6−f+(k-3)*b′ , wherein:
−1≤f≤1;
(c+c′)=1;
(b+b′)=1;
b>0; and
b′>0.

9. The solid electrolyte material of claim 8 , wherein 0.65≤c/(c+c′)≤0.95.

10. The solid electrolyte material of claim 8 , wherein RE comprises Y, and Me′ comprises In, Yb, or Zr.

11. The solid electrolyte material of claim 10 , wherein Me′ is In, and 0.69≤c/(c+c′)≤0.95.

12. The solid electrolyte material of claim 10 , wherein Me′ is Yb, and 0.65≤c/(c+c′)≤0.89.

13. The solid electrolyte material of claim 10 , wherein Me′ is Zr, and 0.72≤c/(c+c′)≤0.98.

14. The solid electrolyte material of claim 1 , wherein the halide material is represented by Li a M a′ REX 6 , wherein:
a>a′>0;
a+a′=3;
0.942≤a/(a+a′)≤0.958; and
RE is at least one rare earth element.

15. The solid electrolyte material of claim 14 , wherein M comprises Na, and X comprises Cl.

16. A solid electrolyte material, comprising a halide material represented by Li a M a′ RE b Me′ b′ Cl c X′ c′ ,
wherein:
M is at least one alkali metal element other than Li;
RE is at least one rare earth element;
Me′ is different from M and Me and includes a divalent, tetravalent element, a trivalent element, or a combination thereof, wherein Me′ has a smaller ionic radius than RE; and
X′ is a halogen other than Cl;
a>0;
a′≥0;
b≥b′>0; and
c≥c′>0;

wherein the halide material has a crystallography phase transition when (b/(b+b′)) t *0.84<b/(b+b′) <(b/(b+′)) t *1.16, wherein (b/(b+b′)) t corresponds to a crystallography phase transition boundary on the crystallography phase diagram at a temperature from 20° C. to 25° C., wherein the crystallography phase transition includes a transition from Pnma or P-3 m1 to C2/m or C2/c, or a transition from orthorhombic to monoclinic crystallography; and
wherein the halide material comprises a total content of at least 0.0001 wt % and not greater than 2 wt % of binary halide phase for a total weight of the halide material, wherein the binary halide phase comprises lithium halide, rare-earth halide, or a combination thereof.

17. The solid electrolyte material of claim 16 , wherein the halide material comprises a total content of a water insoluble impurity phase of less than 0.11 wt % for the total weight of the halide material.

18. A solid electrolyte material, comprising a halide material represented by Li 3−x−f M f RE 1−y Me k y (Cl 1−u−p Br u F p ) 6−x+y*(k−3) ,
wherein:
−1≤x≤1;
0≤y≤1;
0≤u<1;
0≤p≤1/3;
0< (u+p)<1;
0≤f≤0.3;
M is at least one alkali metal element other than Li;
RE is at least one rare-earth element;
k is a valence of Me; and
Me includes a metal element different from RE and M; and

wherein the halide material comprises for a total weight of the halide material:
a total content of one or more water insoluble impurity phase of less than 0.11 wt % and a total content of binary halide phase of at least 0.0001 wt % and not greater than 2 wt %, wherein the binary halide phase comprises lithium halide, rare-earth halide, or a combination thereof.

19. The solid electrolyte material of claim 18 , wherein the halide material is represented by Li 3 Me 3+ Cl 6(1−p) F 6p , wherein 0<p<0.58.

20. The solid electrolyte material of claim 18 , wherein the halide material is represented by Li 3−x RE 1−y Me k y (Cl 1−u Br u ) 6−x+y*(k−3) , wherein 0.08≤u≤0.67.

Assignees

• Saint Gobain Ceramics

Inventors

• Assat Gaurav
• Ouspenski Vladimir

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M2300/0068

  inorganic · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/008

  Halides · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title