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

Patent metadata

Field	Value
Publication number	US-10439251-B2
Application number	US-201715730583-A
Country	US
Kind code	B2
Filing date	Oct 11, 2017
Priority date	Oct 7, 2013
Publication date	Oct 8, 2019
Grant date	Oct 8, 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. A sintered film comprising:
a first layer comprising a sintered lithium-stuffed garnet; and
a second layer in direct contact with the first layer, the second layer comprising a sintered metal;
wherein the sintered film thickness is less than 200 μm and greater than 1 nm.

2. The film of claim 1 , wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li A La B M′ C M″ D Zr E O F , Li A La B M′ C M″ D Ta E O F , and 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<2.5, 10<F<14, and wherein M′ and M″ are each, independently, selected from the group consisting of Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta.

3. The film of claim 1 , wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li A La B Zr C Al D Me″ E O F wherein 4<A<8.5, 1.5<B<4, 0≤C≤2.5, 0≤D≤2, 0≤E<2, and 10<F<14, and wherein Me″ is a metal selected from the group consisting of Nb, Ta, W, Mo, and Sb.

4. The film of claim 3 , wherein E=0.

5. The film of claim 4 , wherein 10<F<13.

6. The film of claim 3 , wherein A<7.

7. The film of claim 4 , wherein 0.3<D<1.

8. The film of claim 5 , wherein 0.3<D<1.

9. The film of claim 1 , wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li x La 3 Zr 2 O 12 .y½Al 2 O 3 ; wherein 5.0<x<9 and 0.1<y<1.5.

10. The film of claim 9 , wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li x La 3 Zr 2 O 12 .0.35Al 2 O 3 .

11. The film of claim 9 , wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li x La 3 Zr 2 O 12 .0.5Al 2 O 3 .

12. The film of claim 9 , wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li 7 La 3 Zr 2 O 12 .0.5Al 2 O 3 .

13. The film of claim 1 , wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li x La 3 Zr 2 O 12 +yAl 2 O 3 ; wherein 5.5≤x≤9, and 0≤y≤1.

14. The film of claim 13 , wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li x La 3 Zr 2 O 12 .Al 2 O 3 .

15. The film of claim 13 , wherein the lithium-stuffed garnet comprises Li 7 La 3 Zr 2 O 12 .0.35Al 2 O 3 .

16. The film of claim 13 , wherein the lithium-stuffed garnet comprises Li 7 La 3 Zr 2 O 12 .0.65Al 2 O 3 .

17. The film of claim 1 , wherein the lithium-stuffed garnet comprises Li 7 La 3 Zr 2 O 12 .0.67Al 2 O 3 .

18. The film of claim 1 , wherein the lithium-stuffed garnet comprises Li 7 La 3 Zr 2 O 12 .Al 2 O 3 .

19. The film of claim 1 , wherein the lithium-stuffed garnet comprises Li 7 La 3 Zr 2 O 12 doped with alumina.

20. The film of claim 1 , wherein the film has a conductivity greater than 10 −4 S/cm at room temperature.

21. The film of claim 1 , wherein the metal of the second layer is nickel, aluminum, iron, steel, stainless steel, copper, an alloy of nickel, an alloy of copper, an alloy of iron, an alloy of aluminum, an alloy of steel, or a combination thereof.

22. The film of claim 1 , wherein the lithium-stuffed garnet of has a median grain size of between 0.5 nm and 10 μm.

23. The film of claim 1 , wherein the lithium-stuffed garnet of has a median grain size of between 10 nm and 10 μm.

24. The film of claim 1 , wherein the lithium-stuffed garnet of has a median grain size of between 100 nm and 10 μm.

25. The film of claim 1 , wherein the sintered film thickness is between 100 nm and 30 μm.

26. The film of claim 1 , wherein the porosity of first layer is less than 20%.

27. The film of claim 1 , wherein the porosity of the first layer is less than 10%.

28. The film of claim 1 , wherein the porosity of first layer is less than 5%.

29. The film of claim 1 , wherein the porosity of first layer is less than 3%.

30. The film of claim 1 , wherein the film has an area specific resistance (ASR) of less than 100 Ωcm 2 at 80° C. when bonded to lithium.

31. The film of claim 1 , further comprising a sintered third layer, the third layer comprising a lithium-stuffed garnet, and the third layer interfacing the second layer.

32. The film of claim 31 , wherein the lithium-stuffed garnet of the third layer comprises at least one member selected from the group consisting of Li x La 3 Zr 2 O 12 .y½Al 2 O 3 ; wherein 5.0<x<9 and 0.1<y<1.5.

33. The film of claim 31 , wherein the lithium-stuffed garnet of the third layer comprises at least one member selected from the group consisting of Li x La 3 Zr 2 O 12 .0.35Al 2 O 3 .

34. The film of claim 31 , wherein the lithium-stuffed garnet of the third layer comprises Li 7 La 3 Zr 2 O 12 .0.35Al 2 O 3 .

35. The film of claim 31 , wherein the lithium-stuffed garnet of the third layer comprises Li 7 La 3 Zr 2 O 12 doped with alumina.

36. The film of claim 31 , wherein the film has a conductivity greater than 10 −4 S/cm at room temperature.

Assignees

• Quantumscape Corp

Inventors

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

Classifications

• C04B35/65

  Reaction sintering of free metal- or free silicon-containing compositions {(C04B35/573, C04B35/591 take precedence)} · CPC title

• C04B2235/3208

  Calcium oxide or oxide-forming salts thereof, e.g. lime · CPC title

• C04B2235/3227

  Lanthanum oxide or oxide-forming salts thereof · CPC title

• C04B2235/96

  Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance · CPC title

• C04B2235/3217

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