Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride
Set forth herein are compositions comprising A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ), 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·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ) compositions. Also disclosed herein are electrochemical devices which incorporate A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ) compositions and other materials.
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.