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

Patent metadata

Field	Value
Publication number	US-11011796-B2
Application number	US-201716343365-A
Country	US
Kind code	B2
Filing date	Oct 20, 2017
Priority date	Oct 21, 2016
Publication date	May 18, 2021
Grant date	May 18, 2021

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≤B≤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 substrate comprising a first layer, wherein the first layer comprises:
A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ),
wherein X is fluorine, bromine, chlorine, or iodine, and
wherein 2.5<A<3.5, 1.5<B<2.5, and 2.5<C<3.5.

2. The substrate of claim 1 , wherein X is chlorine.

3. The substrate of claim 1 , wherein X is bromine.

4. The substrate of claim 1 , wherein X is iodine.

5. The substrate of claim 2 , wherein the first layer is 3LiBH 4 ·2LiCl·3LiNH 2 or 3LiBH 4 ·4LiCl·9LiNH 2 .

6. The substrate of claim 3 , wherein the first layer is 3LiBH 4 ·2LiBr·3LiNH 2 or 3LiBH 4 ·4LiBr·9LiNH 2 .

7. The substrate of claim 4 , wherein the first layer is 3LiBH 4 ·2LiI·3LiNH 2 or 3LiBH 4 ·4LiI·9LiNH 2 .

8. The substrate of claim 1 , further comprising a second layer, wherein the second layer comprises an oxide, a sulfide, a sulfide-halide, or a combination thereof.

9. The substrate of claim 8 , wherein the second layer comprises a sulfide or sulfide-halide selected from LSS, SLOPS, LSTPS, SLOBS, LATS, or LPS+X, wherein X is selected from the group consisting of Cl, I, and Br.

10. The substrate of claim 9 wherein the LPS+X is LPSI.

11. The substrate of claim 8 , wherein the sulfide is a lithium sulfide characterized by one of the following formula:
Li a Si b Sn c P d S e O f , wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, b+c=1, 0.5≤d≤2.5, 4≤e≤12, and 0<f≤10;
Li a Si b P c S d X e , wherein 8<a<12, 1<b<3, 1<c<3, 8<d<14, and 0<e<1, wherein X is F, Cl, Br, or I;
Li g As h Sn j S k O l , wherein 2≤g≤6, 0≤h≤1, 0≤j≤1, 2≤k≤6, and 0≤l≤10;
Li m P n S p I q , wherein 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6;
a mixture of (Li 2 S):(P 2 S 5 ) having a molar ratio of Li 2 S:P 2 S 5 from about 10:1 to about 6:4 and LiI, wherein the ratio of [(Li 2 S):(P 2 S 5 )]:LiI is from 95:5 to 50:50;
LPS+X, wherein X is selected from Cl, I, or Br;
vLi 2 S+wP 2 S 5 +yLiX;
vLi 2 S+wSiS 2 +yLiX; or
vLi 2 S+wB 2 S 3 +yLiX.

12. The substrate of claim 8 , wherein the composition comprises:
a mixture of LiI and Al 2 O 3 ;
Li 3 N;
a mixture of LiBH 4 and LiX wherein X is selected from Cl, I, or Br; or
vLiBH 4 +wLiX+yLiNH 2 , wherein X is selected from Cl, I, or Br; and
wherein coefficients v, w, and y are rational numbers from 0 to 1.

13. The substrate of claim 8 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La y 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.

14. The substrate of claim 8 , 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.

15. The substrate of claim 8 , 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.

16. The substrate of claim 8 , 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.

17. The substrate of claim 1 , wherein the substrate is a thin film and wherein the thin film has a porosity less than 5 percent.

18. The substrate of claim 1 , wherein the substrate has grains with a d 90 grain size of less than 10 μm.

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

20. A method for making a thin film comprising the substrate of claim 1 , comprising:
(a) providing a powder mixture, wherein the mixture comprises:
A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 );
wherein X is F, Br, Cl, or I; and
wherein 2.5<A<3.5, 1.5<B<2.5, and 2.5<C<3.5;

(b) dropping, casting, or spraying the powder mixture on a substrate;
(c) heating the powder mixture with substrate to the mixture melting point but lower than the powder mixture decomposition temperature; and
(d) cooling the substrate to room temperature.

Assignees

• Quantumscape Corp
• Quantumscape Battery Inc

Inventors

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

Classifications

• H01M10/0525 Primary

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

• H01M50/494

  Tensile strength · CPC title

• H01M50/491

  Porosity · CPC title

• H01M50/489

  Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties · CPC title

• H01M50/431 Primary

  Inorganic material · CPC title