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

Patent metadata

Field	Value
Publication number	US-10103405-B2
Application number	US-201715489688-A
Country	US
Kind code	B2
Filing date	Apr 17, 2017
Priority date	Oct 7, 2013
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

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.

First claim

What is claimed is:

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.

Assignees

• Quantumscape Corp

Inventors

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

Classifications

• C04B35/62218

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

• C04B2235/6025

  Tape casting, e.g. with a doctor blade · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• C04B35/6262

  of calcined, sintered clinker or ceramics · CPC title