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 multilayer, comprising:
a first layer comprising a sintered lithium-stuffed garnet polycrystalline thin film, wherein the thickness of the first layer is less than 100 μm and greater than 10 nm; and
a second layer comprising a metal foil or metal powder, wherein the second layer is in contact with the first layer, and wherein the metal foil or metal powder comprises a metal selected from nickel (Ni), copper (Cu), an alloy thereof, and a combination thereof.
2. The multilayer of claim 1 , further comprising a third layer comprising a sintered lithium-stuffed garnet polycrystalline thin film, wherein the thickness of the third layer is less than 100 μm and greater than 10 nm, wherein the second layer is between and in contact with the first layer and the third layer.
3. The multilayer of claim 2 , comprising a layer comprising a positive electrode, a current collector, or a combination thereof in contact with the third layer.
4. The multilayer of claim 2 , wherein thickness of the film in the first layer or in the third layer, or both, is less than 50 μm and greater than 10 nm.
5. The multilayer of claim 2 , wherein the film in the first layer or in the third layer, or both, has grains having a d 50 grain size of between 0.1 μm and 10 μm.
6. The multilayer of claim 5 , wherein the film in the first layer or in the third layer, or both, has grains having a d 50 grain size less than 2 μm.
7. The multilayer of claim 5 , wherein the film in the first layer or in the third layer, or both, has grains having a d 50 grain size less than 1 μm.
8. The multilayer of claim 2 , wherein the film in the first layer or in the third layer, or both, is at least 1 cm in length.
9. The multilayer of claim 8 , wherein the film in the first layer or in the third layer, or both, is at least 10 cm in length.
10. The multilayer of claim 2 , wherein the form factor of the film in the first layer or in the third layer, or both, has a top surface area of 10 cm 2 .
11. The multilayer of claim 2 , wherein the film in the first layer or in the third layer, or both, 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.
12. The multilayer of claim 2 , wherein the film in the first layer or in the third layer, or both, 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.
13. The multilayer of claim 2 , wherein the film in the first layer or in the third layer, or both, 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.
14. The multilayer of claim 2 , wherein the film in the first layer or in the third layer, or both, comprises a lithium-stuffed garnet characterized by the formula Li 7 La 3 Zr 2 O 12 .Al 2 O 3 .
15. The multilayer of claim 2 , wherein the film in the first layer or in the third layer, or both, comprises a lithium-stuffed garnet characterized by the formula Li 7 La 3 Zr 2 O 12 .0.35Al 2 O 3 .
16. The multilayer of claim 2 , further comprising a fourth layer comprising a porous lithium-stuffed garnet polycrystalline thin film, wherein the thickness of the fourth layer is less than 100 μm and greater than 10 nm, wherein the first layer is between and in contact with the second layer and the fourth layer.
17. The multilayer of claim 16 , wherein the fourth layer is infiltrated with at least one member selected from the group consisting of carbon, a lithium conducting polymer, a cathode active material, and combinations thereof.
18. The multilayer of claim 1 , wherein the second layer is a metal powder.
19. The multilayer of claim 1 , wherein the second layer is a metal foil.
20. The multilayer of claim 19 , wherein the metal is Cu.
21. The multilayer of claim 19 , wherein the metal is Ni.
22. The multilayer of claim 1 , comprising a layer comprising a positive electrode, a current collector, or a combination thereof.
23. The multilayer of claim 22 , wherein the positive electrode, a current collector, or a combination thereof is in contact with the first layer.
24. The multilayer of claim 23 , wherein the positive electrode, a current collector, or a combination thereof is not in contact with the second layer.
25. An energy storage device comprising the multilayer of claim 1 .
26. A stack comprising two or more multilayers of claim 1 , wherein the multilayers are stacked in series.