Lithium stuffed garnet setter plates for solid electrolyte fabrication

Patent metadata

Field	Value
Publication number	US-10746468-B2
Application number	US-201715787623-A
Country	US
Kind code	B2
Filing date	Oct 18, 2017
Priority date	Apr 16, 2015
Publication date	Aug 18, 2020
Grant date	Aug 18, 2020

Abstract

Setter plates are fabricated from Li-stuffed garnet materials having the same, or substantially similar, compositions as a garnet Li-stuffed solid electrolyte. The Li-stuffed garnet setter plates, set forth herein, reduce the evaporation of Li during a sintering treatment step and/or reduce the loss of Li caused by diffusion out of the sintering electrolyte. Li-stuffed garnet setter plates, set forth herein, maintain compositional control over the solid electrolyte during sintering when, upon heating, lithium is prone to diffuse out of the solid electrolyte.

First claim

What is claimed is:

1. A method of using a setter plate to fabricate a Li-stuffed garnet solid electrolyte film for a rechargeable battery, the method comprising:
placing a green film comprising unsintered Li-stuffed garnet between two setter plates; and
sintering the green film between and in contact with the two setter plates;
wherein each of the two setter plates comprises at least two members selected from the group consisting of Li 2 ZrO 3 , Li 2 SiO 3 , LiLaO 2 , LiAlO 2 , Li 2 O, Li 3 PO 4 , and a Li-stuffed garnet compound 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 each, independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta; wherein at least one setter plate comprises a Li-stuffed garnet;
wherein the thickness of each of the two setter plates is about 0.1 mm to about 100 mm.

2. The method of claim 1 , further comprising placing a metal foil or metal powder between at least one setter plate and the green film prior to the sintering the green film.

3. The method of claim 1 , wherein the green film has a surface defined by a first lateral dimension from 1 cm to 50 cm and a second lateral dimension from 1 cm to 50 cm.

4. The method of claim 1 , wherein the sintering comprises heating the green film and the two setter plates and exposing the green film and the two setter plates to an Argon:H 2 mixed atmosphere.

5. The method of claim 1 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 100 microns thick and more than 1 nm thick.

6. The method of claim 1 , wherein the sintered Li-stuffed garnet solid electrolyte produced has an ASR between 0.5 Ω·cm 2 to 10 Ω·cm 2 at 50° C.

7. The method of claim 1 , wherein the green film is a tape-cast film.

8. The method of claim 1 , wherein a sintering atmosphere comprises Air, Argon, Nitrogen, an Argon:H 2 mixture, or an Argon:H 2 :H 2 O mixture.

9. The method of claim 2 , wherein the metal is Ni, Cu, Fe, Al, Ag, an alloy of Ni, an alloy of Cu, an alloy of Fe, an alloy of Al, an alloy of Ag, or a combination thereof.

10. The method of claim 1 , wherein the green film has a thickness between 1 μm to about 100 μm.

11. The method of claim 1 , wherein the sintering comprises heating the green film and the two setter plates to between 450° C. and 1300° C.

12. The method of claim 1 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 50 μm thick.

13. The method of claim 1 , further comprising providing a rechargeable battery comprising the Li-stuffed garnet solid electrolyte.

14. A method of using a Li-stuffed garnet setter plate to fabricate a Li-stuffed garnet solid electrolyte film for a rechargeable battery, the method comprising:
placing a green film of unsintered Li-stuffed garnet precursor materials on top of a Li-stuffed garnet setter plate,
wherein the Li-stuffed garnet setter plate 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 each, independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta and at least one member selected from the group consisting of Li 2 ZrO 3 , Li 2 SiO 3 , LiLaO 2 , LiAlO 2 , Li 2 O, Li 3 PO 4 , and a Li-stuffed garnet compound 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 each, independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta; and
sintering the green film on top of the Li-stuffed garnet setter plate to form a sintered garnet film.

15. The method of claim 14 , further comprising placing a metal foil or metal powder between at least one setter plate and the green film prior to the sintering the green film.

16. The method of claim 15 , wherein the metal is Ni, Cu, Fe, Al, Ag, an alloy of Ni, an alloy of Cu, an alloy of Fe, an alloy of Al, an alloy of Ag, or a combination thereof.

17. The method of claim 14 , wherein the green film has a surface defined by a first lateral dimension from 1 cm to 50 cm and a second lateral dimension from 1 cm to 50 cm.

18. The method of claim 14 , wherein the green film has a surface defined by a first lateral dimension from 1 cm to 30 cm and a second lateral dimension from 1 cm to 30 cm.

19. The method of claim 14 , wherein the green film has a thickness between 1 μm to about 100 μm.

20. The method of claim 19 , wherein the green film has a thickness between 1 μm to 80 μm.

21. The method of claim 14 , wherein the sintering comprises heating the green film and Li-stuffed garnet setter plate to between 450° C. and 1300° C.

22. The method of claim 14 , wherein the sintering comprises exposing, during the heating, the green film and the Li-stuffed garnet setter plate to an Argon:H 2 mixed atmosphere.

23. The method of claim 14 , wherein the sintering comprises exposing, during the heating, the green film and the Li-stuffed garnet setter plate to an Argon atmosphere.

24. The method of claim 14 , wherein the green film is a tape-cast green film.

25. The method of claim 14 , wherein the sintering comprises exposing, during the heating, the tape-cast green film and the Li-stuffed garnet setter plate to an Argon:H 2 H 2 O mixed atmosphere.

26. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 100 microns thick and more than 1 nm thick.

27. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 80 microns thick.

28. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 70 microns thick.

29. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 60 microns thick.

30. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 50 microns thick.

31. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 40 microns thick.

32. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 30 microns thick.

33. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced is less than 20 microns thick.

34. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced has an ASR from between 0.5 Ω·cm 2 to 10 Ω·cm 2 at 50° C.

35. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced has an ASR from less than 10 Ω·cm 2 at 50° C.

36. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced has an ASR from less than 10 Ω·cm 2 at 0° C.

37. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced has an ASR from less than 20 Ω·cm 2 at −30° C.

38. The method of claim 14 , wherein the sintered Li-stuffed garnet solid electrolyte produced has an ASR from less than 20 Ω·cm 2 at −30° C. but more than 1 Ω·cm 2 .

39. The method of claim 14 , wherein

Assignees

• Quantumscape Corp

Inventors

• Iyer Sriram
• Holme Tim
• Donnelly Niall

Classifications

• F27B17/02

  specially designed for laboratory use · CPC title

• C04B35/48

  based on zirconium or hafnium oxides, zirconates, {zircon} or hafnates · CPC title

• F27D5/0006 Primary

  Composite supporting structures · CPC title

• C04B35/10 Primary

  based on aluminium oxide · CPC title

• H01M10/056

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title