Garnet materials for Li secondary batteries and methods of making and using garnet materials
Disclosed 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 disclosed herein are lithium-stuffed garnet thin films having fine grains therein. Also disclosed herein are 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 electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Also disclosed herein are methods for preparing 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 disclosed herein are sintering techniques, e.g., for heating and/or field assisted (FAST) sintering, for solid state energy storage devices and the components thereof.
1. An electrode comprising:
a metal foil or metal powder;
two thin and sintered lithium-stuffed garnet films, wherein the film thickness of each thin and sintered lithium-stuffed garnet film is, independently in each instance, less than 50 μm and greater than 10 nm, wherein each film comprises, independently in each instance, a lithium-stuffed garnet characterized by the formula Li A La B M′ C M″ D Zr E O F , Li A La B M′ C M″ D Ta E O F , or Li A La B M′ C M″ D Nb 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 each, independently in each instance, selected from Al, Mo, V, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta;
wherein the metal foil or metal powder is between, and in direct contact with, the two thin and sintered lithium-stuffed garnet films.
2. The electrode of claim 1 , wherein M″ is selected from Nb, Ta, V, W, Mo, and Sb.
3. The electrode of claim 1 , wherein subscripts C, D, and E sum to 2.
4. The electrode of claim 1 , wherein each film has, independently in each instance, a surface roughness of less than 5 μm.
5. The electrode of claim 1 , wherein each thin and sintered lithium-stuffed garnet film comprises, independently in each instance, lithium-stuffed garnet grains having a d 50 median grain size of between 0.1 μm and 10 μm.
6. The electrode of claim 1 , wherein each thin and sintered lithium-stuffed garnet film has a lithium ion interfacial area specific resistance (ASR) of less than 10 Ωcm 2 .
7. The electrode of claim 1 , wherein each thin and sintered lithium-stuffed garnet film has a lithium ion interfacial area specific resistance (ASR) of less than 10 Ωcm 2 at 80° C.
8. The electrode of claim 1 , wherein the carbon content is less than 5 atomic %.
9. The electrode of claim 1 , wherein each thin and sintered lithium-stuffed garnet film density is greater than 4.8 g/cm 3 .
10. The electrode of claim 1 , wherein each thin and sintered lithium-stuffed garnet film porosity is less than 10%.
11. The electrode of claim 1 , wherein the metal foil or metal powder comprises a metal selected from Nickel (Ni), Copper (Cu), combinations thereof, and alloys thereof.
12. The electrode of claim 11 , further comprising cathode active materials in contact with the electrode.
13. The electrode of claim 12 , wherein the cathode active materials are in the discharged state.
14. An electrode made by laminating cathode active materials to the electrode of claim 1 .
15. The electrode of claim 14 , wherein the cathode active materials are in the discharged state.
16. An electrode made by laminating lithium metal to the electrode of claim 1 .