Lithium-stuffed garnet electrolytes with secondary phase inclusions

Patent metadata

Field	Value
Publication number	US-11901506-B2
Application number	US-202217709393-A
Country	US
Kind code	B2
Filing date	Mar 30, 2022
Priority date	Jun 23, 2017
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

The instant disclosure sets forth multiphase lithium-stuffed garnet electrolytes having secondary phase inclusions, wherein these secondary phase inclusions are material(s) which is/are not a cubic phase lithium-stuffed garnet but which is/are entrapped or enclosed within a lithium-stuffed garnet. When the secondary phase inclusions described herein are included in a lithium-stuffed garnet at 30-0.1 volume %, the inclusions stabilize the multiphase matrix and allow for improved sintering of the lithium-stuffed garnet. The electrolytes described herein, which include lithium-stuffed garnet with secondary phase inclusions, have an improved sinterability and density compared to phase pure cubic lithium-stuffed garnet having the formula Li7La3Zr2O12.

First claim

The invention claimed is:

1. A bilayer comprising:
a metal foil or metal powder bonded to one side of a sintered lithium-stuffed garnet thin film;
wherein the sintered lithium-stuffed garnet thin film thickness is less than 50 μm and greater than 10 nm;
wherein the sintered lithium-stuffed garnet thin film includes:
a primary cubic phase lithium-stuffed garnet characterized by the chemical formula Li A La B Al C M″ D Zr E O F , wherein 5<A<8; 1.5<B<4; 0.1<C<2; 0<D<2; 1<E<3; 1O<F<13; and M″ is selected from the group consisting of Mo, W, Nb, Y, Ta, Ga, Sb, Ca, Ba, Sr, Ce, Hf, and Rb; and
a secondary phase inclusion;
wherein:
the primary cubic phase lithium-stuffed garnet is present in the sintered lithium-stuffed garnet thin film at about 70-99.9 vol % with respect to the volume of the sintered lithium-stuffed garnet thin film; and
the secondary phase inclusion is present in the sintered lithium-stuffed garnet thin film at about 0.1-30 vol % with respect to the volume of the sintered lithium-stuffed garnet thin film,
wherein the secondary phase inclusion comprises LiAlO 2 present in the bilayer at about 0.1-25 vol %.

2. The bilayer of claim 1 , wherein the metal foil or metal powder is Ni; Al; Fe; stainless steel; an alloy of Ni, Cu, Al, or Fe; or a combination of Ni, Cu, Al, or Fe.

3. The bilayer of claim 1 , wherein the metal foil or metal powder is selected from Ni, Al, Fe, stainless steel, and combinations thereof.

4. The bilayer of claim 1 , wherein the metal foil or metal powder an alloy of Ni, Cu, Al, or Fe; or a combination of Ni, Cu, Al, or Fe.

5. The bilayer of claim 1 , wherein the bilayer comprises a metal foil.

6. The bilayer of claim 5 , wherein the metal foil is a current collector.

7. The bilayer of claim 5 , wherein the metal foil has a thickness of less than 20 μm.

8. The bilayer of claim 5 , wherein the metal foil has a thickness of less than 10 μm.

9. The bilayer of claim 5 , wherein the metal foil has a thickness of less than 5 μm.

10. A trilayer comprising the bilayer of claim 1 , further comprising a second lithium-stuffed garnet thin film in contact with the metal foil or metal powder of the bilayer.

11. The bilayer of claim 1 , wherein the thickness of the lithium-stuffed garnet thin film is less than 30 μm.

12. The bilayer of claim 1 , wherein the thickness of the lithium-stuffed garnet thin film is less than 20 μm.

13. The bilayer of claim 1 , wherein the lithium-stuffed garnet thin film has a surface roughness of less than 5 μm.

14. The bilayer of claim 1 , wherein the lithium-stuffed garnet thin film has a median grain size of between 0.1 μm to 10 μm.

15. The bilayer of claim 1 , wherein the lithium-stuffed garnet thin film has a median grain size of between 1.0 μm to 5.0 μm.

16. An electrochemical stack comprising at least two or more bilayers of claim 1 .

17. The bilayer of claim 1 , wherein primary cubic phase lithium-stuffed garnet characterized by the chemical formula Li 6.25 La 3 Zr 2 O 12 Al 0.25 .

18. The bilayer of claim 1 , wherein the secondary phase inclusion is present in the sintered lithium-stuffed garnet thin film at about 0.1-10 vol % with respect to the volume of the sintered lithium-stuffed garnet thin film.

19. The bilayer of claim 1 , wherein the secondary phase inclusion is present in the sintered lithium-stuffed garnet thin film at about 0.1-5 vol % with respect to the volume of the sintered lithium-stuffed garnet thin film.

20. The bilayer of claim 1 , wherein the secondary phase inclusion comprises LiAlO 2 present in the bilayer at about 3-8 vol %.

Assignees

• Quantumscape Battery Inc

Inventors

• Beck Larry
• Chao Cheng-Chieh
• Cheng Lei
• Donnelly Niall
• Gardner William H
• Holme Tim
• Hudson Will
• Iyer Sriram
• Karpenko Oleh
• Li Yang
• Xu Gengfu

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• C01G25/006

  Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C01P2002/36

  pyrochlore-type (A2B2O7) · CPC title

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title