Lithium-stuffed garnet electrolytes with secondary phase inclusions

Patent metadata

Field	Value
Publication number	US-12074281-B2
Application number	US-202217961195-A
Country	US
Kind code	B2
Filing date	Oct 6, 2022
Priority date	Jun 23, 2017
Publication date	Aug 27, 2024
Grant date	Aug 27, 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 Li 7 La 3 Zr 2 O 12 .

First claim

What is claimed is:

1. A powder comprising:
a primary phase selected from lithium-stuffed garnet; and
a secondary phase comprising Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and Li x Zr y O z wherein 2≤x≤8, 0≤y≤1, and 1≤z≤6.

2. The powder of claim 1 , wherein the primary phase comprises cubic lithium-stuffed garnet.

3. The powder of claim 2 , wherein the primary phase lithium-stuffed garnet is characterized by the 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, 10<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.

4. The powder of claim 3 , wherein M″ is selected from the group consisting of Mo, W, Nb, Y, Ta, and Ga.

5. The powder of claim 1 , wherein the secondary phase d 50 grain size is from 1 μm to 10 μm.

6. The powder of claim 1 , wherein the primary phase lithium-stuffed garnet d 50 grain size is from 0.5 μm to 10 μm.

7. The powder of claim 1 , wherein a d 90 grain size of the primary phase, secondary phase, or both, is from 1 μm to 5 μm.

8. A pellet comprising the powder of claim 1 .

9. A green film comprising the powder of claim 1 .

10. The powder of claim 1 , wherein the secondary phase in the powder comprises 0.1-25 vol % of LiAlO 2 , 0.1-15 vol % of Li 2 ZrO 3 , 0.1-15 vol % of LaAlO 3 , or a combination thereof, as measured by XRD.

11. The powder of claim 1 , wherein the powder comprises pyrochlore at less than 20 vol % as measured by XRD after heated at 850° C. for 2 hours.

12. The powder of claim 1 , wherein the powder comprises crystalline domains of lithium-stuffed garnet, wherein a median crystalline domain has a d 50 median crystalline domain size of 0.5 nm to 10 μm in diameter.

13. The powder of claim 1 , wherein the secondary phase further comprises tetragonal garnet.

14. The powder of claim 1 , wherein the secondary phase further comprises La 2 Zr 2 O 7 , LiAlO 3 , tetragonal garnet, or combinations thereof.

15. The powder of claim 1 , wherein the secondary phase comprises Li x Al y O z wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, and LiZr 2 O 3 .

16. The powder of claim 1 , wherein the secondary phase comprises LiAlO 2 and Li 2 ZrO 3 .

17. The powder of claim 1 , wherein the secondary phase further comprises LaAlO 3 .

18. The powder of claim 1 , wherein the primary phase comprises cubic lithium-stuffed garnet and the secondary phase further comprises tetragonal garnet.

19. The powder of claim 1 , wherein the secondary phase further comprises La 2 (Li 0.5 Al 0.5 )O 4 .

20. The powder of claim 1 , wherein the secondary phase further comprises LiLaO 2 .

21. The powder of claim 1 , wherein the secondary phase comprises LiZr 2 O 3 and further comprises La 2 Zr 2 O 7 .

22. The powder of claim 1 , wherein the secondary phase comprises LiZr 2 O 3 and further comprises La 2 O 3 .

23. The powder of claim 1 , wherein the secondary phase comprises LiZr 2 O 3 and further comprises La 2 (Li 0.5 Al 0.5 )O 4 .

24. The powder of claim 1 , wherein the secondary phase comprises LiZr 2 O 3 and further comprises LiLaO 2 .

25. The powder of claim 1 , wherein the secondary phase comprises LiZr 2 O 3 and further comprises tetragonal garnet.

26. The powder of claim 1 , wherein the powder is characterized by a median particle size of 100 nm to 10 μm.

27. The powder of claim 1 , wherein the powder is characterized by a median particle size is 800 nm to 2 μm.

28. The powder of claim 1 , wherein the primary phase lithium-stuffed garnet d 50 grain size is larger than the secondary phase d 50 grain size.

29. The powder of claim 1 , wherein the secondary phase includes at least two, three, or four types of secondary phase inclusions.

30. The powder of claim 1 , wherein the secondary phase is homogeneously distributed over a volume of 10000 μm 3 or more.

31. The powder of claim 1 , wherein a density of the powder is 4.6-5.2 g/cm 3 as measured by the Archimedes method.

32. The powder of claim 1 , wherein the powder has a total porosity of less than 5 vol % as determined by SEM.

33. A method of making a slurry comprising combining the powder of claim 1 with non-aqueous solvent and binder.

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

• H01M2300/0071

  Oxides · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• H01M10/0525

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

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• C01P2002/74

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