Ion conductive material including halide material, electrolyte including the same, and methods of forming the same

Patent metadata

Field	Value
Publication number	US-11973186-B2
Application number	US-202318296132-A
Country	US
Kind code	B2
Filing date	Apr 5, 2023
Priority date	Apr 14, 2020
Publication date	Apr 30, 2024
Grant date	Apr 30, 2024

Abstract

A solid ion conductive material can include a complex metal halide. The complex metal halide can include at least one alkali metal element. In an embodiment, the solid ion conductive material including the complex metal halide can be a single crystal. In another embodiment, the ion conductive material including the complex metal halide can be a crystalline material having a particular crystallographic orientation. A solid electrolyte can include the ion conductive material including the complex metal halide.

First claim

What is claimed is:

1. A solid ion conductive material, comprising a crystallographically-oriented ceramic material, wherein grains of the crystallographically-oriented ceramic material are oriented in a particular direction; and wherein the crystallographically-oriented ceramic material comprises a halide material represented by M 3−z (Me k+ ) f X 3−z+k*f , wherein:
−3≤z<3;
2≤k<6;
0≤f≤1;
M comprises an alkali metal element;
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;
X comprises a halogen; and
the halide material comprises at least two different cations,

wherein the halide material further comprises:
a total content of simple metal halide of at most 2 wt % for a weight of the halide material, wherein the simple metal halide comprises alkali metal halide, rare earth halide, or any combination thereof;
at least one of electric charge neutral Me x N k or M x N, wherein x is a valence of N and k is the valence of Me; or
any combination thereof.

2. The solid ion conductive material of claim 1 , wherein the halogen is one or more elements selected from the group consisting of Cl, Br, and F.

3. The solid ion conductive material of claim 1 , wherein the halogen consists of at least two or more of Cl, Br, I, and F.

4. The solid ion conductive material of claim 1 , wherein M comprises at least one of Li and Na.

5. The solid ion conductive material of claim 1 , wherein the halide material is represented by Li 3−z Me k+ X 3−z+k , wherein Me comprises a rare earth element, Al, Zr, Hf, In, Mg, Zn, or any combination thereof.

6. The solid ion conductive material of claim 1 , wherein the halide material comprises a total content of simple metal halide of at most 2 wt % for a weight of the halide material, wherein the simple metal halide comprises alkali metal halide, rare earth halide, or any combination thereof.

7. The solid ion conductive material of claim 1 , wherein the crystallographically-oriented ceramic material has a crystallographic orientation represented by <HKL> or <HKLM>, wherein an ionic conductivity in the crystallographic orientation of <HKL> or <HKLM> is higher than an ionic conductivity in a different crystallographic orientation, wherein more than 80% of the grains are oriented in the crystallographic orientation represented by <HKL> or <HKLM>.

8. The solid ion conductive material of claim 1 , wherein the halide material is represented by (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′) , wherein:
0≤d≤1;
0≤e<1;
−3≤z′<3;
M′ includes at least one of K, Rb, or Cs;
M 3+ includes a rare-earth element, In, Bi, Sc, Y, Al, Ga 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;
−0.95<z<0.95;
0≤u<0.95;
0≤p<0.95;
0≤q<0.95;
0≤r<0.95; and
0≤(u+p+q+r)≤1, wherein (d+e)>0 when (u+p+q+r)≤1.

9. The solid ion conductive material of claim 8 , wherein (u+p+q+r)<1, and wherein M 3+ includes Y 3+ , Gd 3+ , In 3+ , Er 3+ , La 3+ , Sc 3+ , or any combination thereof.

10. The solid ion conductive material of claim 8 , wherein u>0, and wherein M 4+ includes Zr 4+ , Hf 4+ , Ce 4+ , or a combination thereof.

11. A solid ion conductive material, comprising a crystallographically-oriented ceramic material, wherein grains of the crystallographically-oriented ceramic material are oriented in a particular direction; and wherein the crystallographically-oriented ceramic material comprises a halide material represented by (Li 1−d−e , Na d , M′ e ) 2 Li 1−z (Me k+ ) f X 3+k*f−z , wherein:
−1≤z<1;
2≤k<6;
0≤f≤1;
0≤d≤1;
0≤e<1;
(d+e+f)>0;
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; and X comprises a halogen; and
M′ consists of at least one of K, Rb, and Cs,
wherein the halide material further comprises:
at least one of electric charge neutral Me x N k or M x N, wherein x is a valence of N and k is the valence of Me;
a total content of simple metal halide of at most 2 wt % for a weight of the halide material, wherein the simple metal halide comprises alkali metal halide, rare earth halide, or any combination thereof; or
a combination thereof.

12. The solid ion conductive material of claim 11 , wherein (d+e)>0, and wherein Li makes up at least 50 mol % for a total of Li, Na, and M′.

13. The solid ion conductive material of claim 11 , comprising a total content of simple metal halide of at most 2 wt % for a weight of the halide material, wherein the simple metal halide comprises alkali metal halide, rare earth halide, or any combination thereof.

14. The solid ion conductive material of claim 11 , wherein the halide material is represented by Li 3−z (Me k+ ) f X 3−z+k*f , wherein 0<f≤1; and X comprises a halogen including at least one of Cl or Br.

15. The solid ion conductive material of claim 11 , further comprising at least one of the electric charge neutral Me x N k or M x N, wherein x is a valence of N and k is the valence of Me.

16. A solid electrolyte layer, comprising a crystallographically-oriented crystalline material comprising a halide material represented by (Li 1−d−e , Na d , M′ e ) 2 Li 1−z (Me k+ ) f X 3+k*f−z , wherein:
−3≤z<3;
2≤k<6;
0≤f≤1;
−3≤z<3;
2≤k<6;
0≤f≤1;
0≤d≤1;
0≤e<1;
(d+e)>0; and
M′ consists of at least one of K, Rb, and C;
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;
X comprises a halogen; and
the halide material comprises at least two different cations,
wherein a crystallographic orientation of the crystallographically oriented crystalline material is in a direction of a thickness of the solid electrolyte layer, wherein an ionic conductivity in the crystallographic orientation is higher than an ionic conductivity in a different crystallographic orientation,
wherein the solid electrolyte layer further comprises:
a total content of simple metal halide of at most 2 wt % for a weight of the halide material, wherein the simple metal halide comprises alkali metal halide, rare earth halide, or any combination thereof;
at least one of electric charge neutral Me x N k or M x N, wherein x is a valence of N and k is the valence of Me; or
any combination thereof.

17. The solid electrolyte layer of claim 16 , wherein the crystallographically-oriented crystalline material is a ceramic material comprising grains having a crystallographic orientation in the direction of the thickness of the solid electrolyte layer.

18. The solid electrolyte layer of claim 16 , wherein the halide material is represented by Li 3−z (Me k+ ) f X 3−z+k*f , wherein 0<f≤1; and X comprises a halogen including at least one of Cl or Br.

19. The solid electrolyte layer of claim 16 ,
wherein the crystallographically-oriented crystalline material is a single-crystal material.

Assignees

• Saint Gobain Ceramics

Inventors

• Ouspenski Vladimir
• Assat Gaurav
• Frank John M

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• C30B23/08

  by condensing ionised vapours (by reactive sputtering C30B25/06) · CPC title

• C30B29/12

  Halides · CPC title

• H01M10/0525

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

• H01M2300/008

  Halides · CPC title