Garnet materials for Li secondary batteries and methods of making and using garnet materials

Patent metadata

Field	Value
Publication number	US-10431850-B2
Application number	US-201715632011-A
Country	US
Kind code	B2
Filing date	Jun 23, 2017
Priority date	Oct 7, 2013
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

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.

First claim

What is claimed is:

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 .

Assignees

• Quantumscape Corp

Inventors

• Choi Dong Hee Anna
• Donnelly Niall
• Holme Tim
• Hudson Will
• Iyer Sriram
• Karpenko Oleh
• Kerman Kian
• Singh Mohit
• Winoto Adrian

Classifications

• C04B2235/3256

  Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate · CPC title

• C04B35/62218

  obtaining ceramic films, e.g. by using temporary supports · CPC title

• C04B2235/3213

  Strontium oxides or oxide-forming salts thereof · CPC title

• C04B35/495

  based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates · CPC title

• C04B2235/3217

  Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina · CPC title