Garnet materials for Li secondary batteries and methods of making and using garnet materials
Set forth herein are garnet material compositions, e.g., lithium-stuffed garnets and lithium-stuffed garnets doped with alumina, which are suitable for use as electrolytes and catholytes in solid state battery applications. Set forth herein are lithium-stuffed garnet thin films having fine grains therein. Disclosed herein are novel and inventive methods of making and using lithium-stuffed garnets as catholytes, electrolytes and/or anolytes for all solid state lithium rechargeable batteries. Disclosed herein are novel electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Set forth herein are methods for preparing novel structures, including dense thin free standing membranes of an ionically conducting material for use as a catholyte, electrolyte, and, or, anolyte, in an electrochemical device, a battery component (positive or negative electrode materials), or a complete solid state electrochemical energy storage device. The methods set forth herein disclose novel sintering techniques for solid state energy storage devices and the components thereof.
1. A composition comprising a lithium-stuffed garnet and Al 2 O 3 , wherein the lithium-stuffed garnet is characterized by the empirical formula Li A La B M′ c M″ D Zr E O F , wherein 4<A<8.5, 1.5<B<4, 0.7≤C≤2, 0=D; 0<E≤2.5, 10<F≤15; M′ is Al; and wherein the composition is a sintered thin film having a film thickness of about 10 nm to about 100 μm.
2. The composition of claim 1 , wherein the composition is characterized by the empirical formula Li x La 3 Zr 2 O 12 .y½Al 2 O 3 ; wherein 6.0<x<8.5 and 0.9<y<1.1.
3. The composition of claim 1 , wherein the composition is characterized by Li 7 La 3 Zr 2 O 12 .Al 2 O 3 .
4. The composition of claim 1 , wherein the composition is characterized by the empirical formula Li 7 La 3 Zr 2 O 12 .0.35 Al 2 O 3 .
5. The composition of claim 1 , wherein A is 5, 6, 7, or 8.
6. The composition of claim 1 , wherein E is 1, 1.5, or 2.
7. The composition of claim 1 , wherein the subscript values represent elemental molar ratios of the precursor chemicals used to make the claimed composition.
8. The composition of claim 1 , wherein the film has grains having a d 50 diameter less than 10 μm.
9. The composition of claim 1 , wherein the film has grains having a d 50 diameter less than 2 μm.
10. The composition of claim 1 , wherein the film has grains having a d 50 diameter less than 1 μm.
11. An energy storage device comprising an electrolyte comprising a composition according to claim 1 .
12. An electrochemical device comprising a catholyte comprising a composition according to claim 1 .