Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride

Patent metadata

Field	Value
Publication number	US-11855251-B2
Application number	US-202318152566-A
Country	US
Kind code	B2
Filing date	Jan 10, 2023
Priority date	Oct 21, 2016
Publication date	Dec 26, 2023
Grant date	Dec 26, 2023

Abstract

Set forth herein are compositions comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X is fluorine, bromine, chloride, iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤13≤4, and 0≤C≤9 that are suitable for use as solid electrolyte separators in lithium electrochemical devices. Also set forth herein are methods of making A·(LiBH4)·B·(LiX)·C·(LiNH2) compositions. Also disclosed herein are electrochemical devices which incorporate A·(LiBH4)·B·(LiX)·C·(LiNH2) compositions and other materials.

First claim

What is claimed is:

1. A composition, comprising:
A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ),
wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, and
wherein 2<A<4, 0.5≤B≤3, 1≤C≤5.

2. The composition of claim 1 wherein A is 3; B is 1; and C is 2.

3. The composition of claim 1 , wherein X is chlorine.

4. The composition of claim 1 , wherein X is bromine.

5. The composition of claim 1 , wherein X is iodine.

6. The composition of claim 1 , wherein the composition is amorphous.

7. The composition of claim 1 , wherein the composition is semi-crystalline.

8. The composition of claim 1 , wherein the composition has a lithium ion conductivity greater than 1×10 −4 S/cm at 60° C.

9. The composition of claim 1 , wherein the composition is a thin film.

10. The composition of claim 1 , further comprising an oxide, a sulfide, a sulfide-halide, or a combination thereof.

11. The composition of claim 9 , wherein the oxide is a lithium-stuffed garnet characterized by the formula Li x La y Zr z O t ·qAl 2 O 3 , wherein 4<x<10, 1<y<4, 1<z<3, 6<t<14, and 0≤q≤1.

12. The composition of claim 11 , wherein the lithium-stuffed garnet is doped with Nb, Ga, and/or Ta.

13. The composition of claim 10 , wherein the oxide is a lithium-stuffed garnet characterized by the formula Li a La b Zr c Al d Me″ e O f , wherein 5<a<8.5; 2<b<4; 0≤c≤2.5; 0≤d<2; 0≤e<2, and 10<f<13 and Me′ is a metal selected from the group consisting of Nb, Ga, Ta, and combinations thereof.

14. The composition of claim 10 , wherein the sulfide or sulfide-halide is selected from LSS, SLOPS, LSTPS, LSTPSCl, SLOBS, LATS, or LPS+X, wherein X is selected from the group consisting of Cl, I, and Br.

15. The composition of claim 10 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y ·zAl 2 O 3 , wherein
u is a rational number from 4 to 8;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14;
z is a rational number from 0.05 to 1; and
wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

16. The composition of claim 10 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y ·zTa 2 O 5 , wherein
u is a rational number from 4 to 10;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14; and
z is a rational number from 0 to 1;
wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

17. The composition of claim 10 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y ·zNb 2 O 5 , wherein
u is a rational number from 4 to 10;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14; and
z is a rational number from 0 to 1;
wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

18. The composition of claim 10 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y ·zGa 2 O 3 , wherein
u is a rational number from 4 to 10;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14; and
z is a rational number from 0 to 1;
wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

19. The composition of claim 10 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y ·zTa 2 O 5 ·bAl 2 O 3 , wherein
u is a rational number from 4 to 10;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14;
z is a rational number from 0 to 1;
b is a rational number from 0 to 1;
wherein z+b<1; and
u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

20. The composition of claim 10 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y ·zNb 2 O 5 ·bAl 2 O 3 , wherein
u is a rational number from 4 to 10;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14;
z is a rational number from 0 to 1;
b is a rational number from 0 to 1;
wherein z+b≤1; and
u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

21. The composition of claim 10 , wherein the oxide is:
a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y ·zGa 2 O 3 ·bAl 2 O 3 , wherein
u is a rational number from 4 to 10;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14; and
z is a rational number from 0 to 1;
b is a rational number from 0 to 1;
wherein z+b≤1; and
u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

Assignees

• Quantumscape Battery Inc

Inventors

• Chen Zhebo
• Holme Tim
• Mayer Marie
• Perkins Nick
• Tulsky Eric
• Chao Cheng-Chieh
• Dekmezian Christopher
• Li Shuang

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/667

  in the form of layers, e.g. coatings · CPC title

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title

• H01M10/0525 Primary

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