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≤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.(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 either:
A is 2; B is 1; and C is 2; or
A is 3; B is 3; and C is 4.
2. The composition of claim 1 , wherein X is chlorine.
3. The composition of claim 1 , wherein X is bromine.
4. The composition of claim 1 , wherein X is iodine.
5. The composition of claim 1 , wherein the composition is amorphous.
6. The composition of claim 1 , wherein the composition is semi-crystalline.
7. The composition of claim 1 , wherein the composition has a lithium ion conductivity greater than 1×10 −4 S/cm at 60° C.
8. The composition of claim 1 , wherein the composition is a thin film.
9. The composition of claim 1 , further comprising an oxide, a sulfide, a sulfide-halide, or a combination thereof.
10. 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.
11. The composition of claim 10 , wherein the lithium-stuffed garnet is doped with Nb, Ga, and/or Ta.
12. The composition of claim 9 , 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.
13. The composition of claim 9 , 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.
14. The composition of claim 9 , 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.
15. The composition of claim 9 , 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.
16. The composition of claim 9 , 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.
17. The composition of claim 9 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zGa 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 9 , 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.
19. The composition of claim 9 , 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.
20. The composition of claim 9 , 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.