Electrolyte material and methods of forming

Patent metadata

Field	Value
Publication number	US-11848414-B2
Application number	US-202217746581-A
Country	US
Kind code	B2
Filing date	May 17, 2022
Priority date	May 17, 2021
Publication date	Dec 19, 2023
Grant date	Dec 19, 2023

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 including at least two halide anions selected from the group consisting of F, Cl, Br, and I and 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:
−1<=x<=1;
0<=y<=1;
0<=u<1;
0<=p<=⅓;
0<=q<=⅙;
0<(u+p+q)<1;
0<=f<=0.3;
M is at least one alkali metal element other than Li;
RE is a rare-earth element;
k is a valence of Me; and
Me is at least one element from the group consisting of Group IIIB elements, Group IVB elements, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge, wherein Me is different from RE; 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 10 wt %, 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 comprises for the total weight of the halide material, not greater than 2 wt % of the binary halide phase.

3. The solid electrolyte material of claim 1 , wherein the one or more water insoluble impurity phase comprises an oxyhalide phase, a metal oxide phase, or a combination thereof.

4. The solid electrolyte material of claim 1 , 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.

5. An electrolyte material, comprising a halide material including at least two halide anions selected from the group consisting of F, Cl, Br, and I within a single phase, wherein the halide material is 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:
−1<=x<=1;
0<=y<=1;
0<=u<1;
0<=p<=⅓;
0<=q<=⅙;
0<(u+p+q)<1;
0<=f<=0.3;
M is at least one alkali metal element other than Li;
RE is a rare-earth element;
k is a valence of Me; and
Me is at least one element selected from the group consisting of Group IIIB elements, Group IVB elements, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge, wherein Me is different from RE,
wherein the halide material comprises a total content of 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.

6. The solid electrolyte material of claim 5 , wherein the halide material comprises for the total weight of the halide material, the total content of not greater than 2 wt % of a binary halide phas, and a total content of one or more water insoluble impurity phase of less than 0.11 wt %.

7. The solid electrolyte material of claim 5 , wherein the halide material comprises a crystalline structure represented by a rhombohedral space group.

8. The solid electrolyte material of claim 5 , wherein the crystalline structure comprises a unit cell that is smaller than the unit cell of Li 3 YBr 6 .

9. The solid electrolyte material of claim 5 , wherein peaks of a powder diffraction pattern of the halide material are shifted to higher angles compared to corresponding peaks of a powder diffraction pattern of Li 3 YBr 6 .

10. The solid electrolyte material of claim 5 , wherein the halide material is represented by Li 3-x-f M f RE 1-y Me k y (Cl 1-p F p ) 6-x+y*(k-3) , wherein 0<=p<2.

11. The solid electrolyte material of claim 5 , wherein RE comprises Y, Ce, Gd, Er, La, or Yb; and Me comprises Y, Ce, Gd, Er, Sm, Eu, Pr, Tb, Al, Zr, La, Yb, Mg, Zn, Sn, Mg, Ca, or any combination thereof, wherein RE is different from Me.

12. The solid electrolyte material of claim 11 , wherein RE consists of Y, and Me is at least one element selected from the group consisting of Gd, Yb, Zr, Zn, Mg, Al, and Ca.

13. The solid electrolyte material of claim 4 , wherein the halide material comprises an average diffraction crystallite size of at least 25 nm.

14. An electrochemical device, comprising:
a solid electrolyte layer comprising the solid electrolyte material of claim 5 , wherein the halide material comprises at least one of Cl and F;
an electrode layer comprising a cathode-active material in contact with the solid electrolyte material,
wherein the solid electrolyte layer is capable of forming a chlorine-deficient or a fluorine-deficient region proximal to the electrode layer under an oxidative condition, wherein the chlorine- or fluorine-deficient region comprises a lower concentration of chlorine or fluorine, respectively, comparing to a region of the solid electrolyte layer that is distal to the electrode layer.

15. A solid electrolyte material, comprising a halide material represented by Li a M a′ Me b′ Me′ b′ X c X′ c′ ,
wherein the halide material has a crystallography phase transition within the stoichiometry range of:
(b/(b+b′)) t *0.84<b/(b+b′)<(b/(b+b′)) t *1.16, wherein (b/(b+b′)) t corresponds to the crystallography phase transition on the crystallography phase diagram at a temperature from 20° C. to 25° C.;
(c/(c+c′)) t *0.84<c/(c+c′)<(c/(c+c′)) t *1.16, wherein (c/(c+c′)) t corresponds to the crystallography phase transition on the crystallography phase diagram at the temperature from 20° C. to 25° C.; or
(a/(a+a′)) t *0.84<a/(a+a′)<(a/(a+a′)) t *1.16, wherein (a/(a+a′)) t corresponds to the crystallography phase transition on the crystallography phase diagram at the temperature from 20° C. to 25° C.;

wherein:
Me is least one element from the group consisting of Group IIIB elements, Group IVB elements, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, In, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge;
Me′ is at least one element other than Me and from the group consisting of Group IIIB elements, Group IVB elements, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, In, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge;
Where b>=b′; c>=c′; a>=a′; X is at least one halogen other than X′;
X′ is a halogen; and
M is at least one alkali metal element other than Li; and

wherein anions of the halide material are within a single phase; and
wherein the halide material comprises a total content or 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.

16. The solid electrolyte material of claim 15 , wherein the crystallography phase transition comprises:
a transition from a layered crystal structure to a non-layered crystal structure;
a transition from a cubic close-packed structure to a hexagonal close-packed structure;
a transition from C2/m space group or R-3m space group to P-3ml or Pnma space group;
a transition from a non-layered crystal structure to another non-layered crystal structure or to a layered crystal structure;

a transition from R3c to R3m; or
a transition from P-3ml or Pnma space group to C2/m space group or R-3m space group; and
wherein the total content of the binary halide phase is not greater than 2 wt % for the total weight of the halide material, and
wherein the halide material comprises a total content of one or more water insoluble impurity phase of less than 0.11 wt %.

17. The solid electrolyte material of claim 15 , wherein the halide material is represented by Li a-f M a′ RE b Me′ k b′ (Cl x Br c′ ) 6-f+(k-3)*b′ , wherein:
a+a′=3;
−1≤f≤1;
c+c′=1; and
b+b′=1; and
wherein the total content of the binary halide phase is not greater than 2 wt % for the total

Assignees

• Saint Gobain Ceramics

Inventors

• Assat Gaurav
• Ouspenski Vladimir

Classifications

• H01M2300/008

  Halides · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M2300/0068

  inorganic · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title