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. Also 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. Also disclosed herein are novel electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Also set forth herein are methods for preparing novel structures, including dense thin (<50 um) 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. Also, the methods set forth herein disclose novel sintering techniques, e.g., for heating and/or field assisted (FAST) sintering, for solid state energy storage devices and the components thereof.
1. A thin and free standing sintered lithium-stuffed garnet polycrystalline film, wherein the film thickness is less than 100 μm and greater than 10 nm, wherein the film has grains having a d 50 grain size less than 10 μm, and wherein the film is not adhered or fixed to a substrate, and wherein the film is at least 1 cm in length.
2. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film is at least 10 cm in length.
3. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the form factor of the thin and free standing sintered lithium-stuffed garnet polycrystalline film has a top surface area of 10 cm 2 .
4. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film thickness is less than 50 μm and greater than 10 nm.
5. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film has grains having a d 50 grain size less than 2 μm.
6. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film has grains having a d 50 grain size less than 1 μm.
7. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film has grains having a median grain size of between 0.1 μm and 10 μm.
8. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film comprises a lithium-stuffed garnet characterized by the formula Li x La 3 Zr 2 O 12 .yAl 2 O 3 , wherein 5.5≤x≤9; and 0<y≤1.
9. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film comprises a lithium-stuffed garnet characterized by the formula Al 2 O 3 :Li x La 3 Zr 2 O 12 , wherein the Al 2 O 3 :Li x La 3 Zr 2 O 12 ratio is 0.35, 0.5, 0.67 or 1.0.
10. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film comprises a lithium-stuffed garnet characterized by the formula Li 7 La 3 Zr 2 O 12 . Al 2 O 3 .
11. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film comprises a lithium-stuffed garnet characterized by the formula Li 7 La 3 Zr 2 O 12 . 0.35 Al 2 O 3 .
12. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film has a surface roughness of less than 5 μm.
13. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film has an area specific resistance (ASR) of less than 10 Ωcm 2 .
14. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film has an area specific resistance (ASR) of less than 10 Ωcm 2 at 80° C.
15. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film has a carbon content that is less than 5 atomic %.
16. An energy storage device comprising an electrolyte comprising the thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 .
17. The thin and free standing sintered lithium-stuffed garnet polycrystalline film of claim 1 , wherein the film comprises a lithium-stuffed garnet characterized by the formula Li A La B M′ c M″ D Zr E O F wherein 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2, 0≤E≤2, 10≤F≤13, and M′ and M″ are independently in each instance either absent or are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta.