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

Patent metadata

Field	Value
Publication number	US-2024213519-A1
Application number	US-202318495873-A
Country	US
Kind code	A1
Filing date	Oct 27, 2023
Priority date	Oct 21, 2016
Publication date	Jun 27, 2024
Grant date	—

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 composition, comprising:
A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ),
wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, and wherein 0.1≤A≤4, 0.1≤B≤5, and 0<C≤9.5.

2 . A composition, comprising:
A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ),
wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0<C≤9.

3 . The composition of claim 1 or 2 , wherein X is bromine, chlorine, iodine, or a combination thereof.

4 . The composition of any one of claims 1-3 , wherein X is chlorine.

5 . The composition of any one of claims 1-3 , wherein X is bromine.

6 . The composition of any one of claims 1-3 , wherein X is iodine.

7 . The composition of any one of claims 1-5 , wherein 2.5<A<3.5, 1.5<B<2.5, and 2.5<C<3.5.

8 . The composition of any one of claims 1-5 , wherein 2.5<A<3.5, 3.5<B<4.5, and 8.5<C<9.5.

9 . The composition of any one of claims 1-3 wherein the composition is 3LiBH 4 ·2LiCl·3LiNH 2 or 3LiBH 4 ·4LiCl·9LiNH 2 .

10 . The composition of any one of claims 1-3 and 5 , wherein the composition is 3LiBH 4 ·2LiBr·3LiNH 2 or 3LiBH 4 ·4LiBr·9LiNH 2 .

11 . The composition of any one of claims 1-3 and 6 , wherein the composition is 3LiBH 4 ·2LiI·3LiNH 2 or 3LiBH 4 ·4LiI·9LiNH 2 .

12 . The composition of any one of claims 1-11 , wherein the composition is amorphous.

13 . The composition of any one of claims 1-11 , wherein the composition is semi-crystalline.

14 . The composition of any one of claims 1-13 , wherein the composition has a lithium ion conductivity greater than 1×10 −4 S/cm at 60° C.

15 . The composition of any one of claims 1-14 , wherein the composition has grains with a d 90 grain size of less than 20 μm.

16 . The composition of any one of claims 1-15 , wherein the composition has grains with a d 90 grain size of less than 10 μm.

17 . The composition of any one of claims 1-16 , wherein the composition has grains with a d 90 grain size of less than 5 μm.

18 . The composition of any one of claims 1-17 , wherein the composition has grains with a d 90 grain size of less than 2 μm.

19 . The composition of any one of claims 1-18 , wherein the composition has grains with a d 90 grain size of less than 1 μm.

20 . The composition of any one of claims 1-19 , wherein the composition is a thin film.

21 . The composition of any one of claims 1-19 , wherein the composition is a monolith.

22 . The composition of any one of claims 1-19 , wherein the composition is a pressed pellet.

23 . The composition of any one of claims 1-22 , further comprising an oxide, a sulfide, a sulfide-halide, or a combination thereof.

24 . The composition of any one of claims 1-23 , further comprising an electrolyte.

25 . The composition of claim 20 , 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.

26 . The composition of claim 25 , wherein the lithium-stuffed garnet is doped with Nb, Ga, and/or Ta.

27 . The composition of claim 23 , wherein the oxide is a lithium-stuffed garnet characterized by the formula Li a La b Zr e 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.

28 . The composition of claim 23 , wherein the sulfide or sulfide-halide is selected from LSS, SLOPS, LSTPS, LSTPSCI, SLOBS, LATS, or LPS+X, wherein X is selected from the group consisting of Cl, I, and Br.

29 . The composition of claim 23 , wherein the sulfide or sulfide-halide is selected from LSS, SLOPS, LSTPS, SLOBS, LATS, or LPS+X, wherein X is selected from the group consisting of Cl, I, and Br.

30 . The composition of claim 23 wherein the LPS+X is LPSI.

31 . The composition of claim 23 , 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.

32 . The composition of claim 23 , 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, O≤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.

33 . The composition of claim 23 or 32 , 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.

34 . The composition of claim 24 , wherein the electrolyte is selected from the group consisting of:
LIRAP; LATP; LAGP; 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; 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.

35 . The composition of claim 23 , 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.

36 . The composition of claim 23 , 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.

37 . The composition of claim 23 , 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.

38 . The comp

Assignees

• Quantumscape Battery Inc

Inventors

• Chen Zhebo
• Holme Timothy
• Mayer Marier
• 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

• H01M50/491

  Porosity · CPC title