Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-2019245178-A1
Application number	US-201716343361-A
Country	US
Kind code	A1
Filing date	Oct 19, 2017
Priority date	Oct 21, 2016
Publication date	Aug 8, 2019
Grant date	—

Abstract

The disclosure herein relates to rechargeable batteries and solid electrolytes therefore which include lithium-stuffed garnet oxides, for example, in a thin film, pellet, or monolith format wherein the density of defects at a surface or surfaces of the solid electrolyte is less than the density of defects in the bulk. In certain disclosed embodiments, the solid-state anolyte, electrolyte, and catholyte thin films, separators, and monoliths consist essentially of an oxide that conducts Li+ ions. In some examples, the disclosure herein presents new and useful solid electrolytes for solid-state or partially solid-state batteries. In some examples, the disclosure presents new lithium-stuffed garnet solid electrolytes and rechargeable batteries which include these electrolytes as separators between a cathode and a lithium metal anode.

First claim

1 . A separator comprising a lithium-stuffed garnet and having top and bottom surfaces and a bulk therebetween,
wherein either or both of the top or bottom surfaces has a lower surface defect density than does the bulk.

2 . The separator of claim 1 , wherein the top or bottom surface has a lower areal surface defect density than does the bulk.

3 . The separator of claim 1 or 2 , wherein the ninety-ninth (99 th ) percentile pore aspect ratio of the pores on the top or bottom surface is less than the ninety-ninth (99 th ) percentile pore aspect ratio of the pores in the bulk.

4 . The separator of any one of claims 1 - 3 , wherein the ninety-ninth (99 th ) percentile pore aspect ratio of the pores on the top or bottom surface is less than 10 and greater than 0.1.

5 . The separator of claim 4 , wherein the ninety-ninth (99 th ) percentile pore aspect ratio of the pores on the top or bottom surface is less than 4, less than 4.5, less than 4.0, less than 3.5, less than 3.0, less than 2.5, less than 2.0, less than 1.5, less than 1, or less than 0.5.

6 . The separator of any one of claims 1 - 5 , wherein the top or bottom surface is more dense than the bulk.

7 . The separator of any one of claims 1 - 5 , wherein the top or bottom surface is less crystalline than the bulk.

8 . The separator of any one of claims 1 - 5 , wherein the grain size at the top or bottom surface is larger than the grain size in the bulk.

9 . The separator of any one of claims 1 - 8 , wherein the separator is a thin film.

10 . The separator of claim 9 , wherein the thickness between the top and bottom surfaces is between 1 nm and 100 nm.

11 . The separator of claim 1 , wherein the defect density is a density of inclusions.

12 . A thin film lithium-stuffed garnet electrolyte, wherein the thin film is substantially homogenous within x- and y-dimensions; and wherein the thin film is inhomogeneous with respect to the z-dimension.

13 . The thin film of claim 12 , wherein the inhomogeneity with respect to the z-dimension is a surface defect density inhomogeneity.

14 . The thin film of claim 12 wherein the inhomogeneity with respect to the z-dimension is a porosity inhomogeneity.

15 . The thin film of claim 12 , wherein the inhomogeneity with respect to the z-dimension is a grain size inhomogeneity.

16 . The thin film of claim 12 , wherein the inhomogeneity with respect to the z-dimension is an inhomogeneity regarding the ninety-ninth (99 th ) percentile aspect ratios of the pores on the top or bottom surface as compared to in the bulk.

17 . The thin film of claim 12 , wherein the inhomogeneity with respect to the z-dimension is an inhomogeneity regarding the average aspect ratios of the pores.

18 . The thin film of claim 12 , wherein the inhomogeneity with respect to the z-dimension is an inhomogeneity regarding the density of the pores.

19 . The thin film of claim 12 , wherein the inhomogeneity with respect to the z-dimension is an inhomogeneity regarding the oxygen vacancy concentration.

20 . An electrochemical stack comprising the separator of any one of claims 1 - 10 , or the thin film of any one of claims 12 - 19 .

21 . A process for selectively reducing the number and/or size of surface-pores and defects on a lithium-stuffed garnet separator, the method comprising:
providing a sintered separator comprising a lithium-stuffed garnet; heating the top and/or bottom surfaces of the separator above the melting temperature; and rapidly cooling the separator below the melting temperature.

22 . The process of claim 21 , further comprising adding lithium-stuffed garnet precursors on the top and/or bottom surface prior to the heating step.

23 . The process of claim 21 , wherein the lithium-stuffed garnet precursors are powders

24 . The process of any one of claims 21 - 23 , wherein the heating is for the minimal time period required to melt the top and/or bottom surface.

25 . The process of any one of claims 21 - 24 , wherein the cooling is for the longest time which still provides for smaller grains on the top or bottom surface than in the bulk.

26 . The process of any one of claims 21 - 24 , wherein the cooling is for the longest time which still provides for a top and/or bottom surface which is denser than the bulk.

27 . The process of any one of claims 21 - 24 , wherein the cooling is for the longest time which still provides for a top and/or bottom surface which is less crystalline than the bulk.

28 . The process of any one of claims 21 - 27 , wherein the heating is to 1325° C.

29 . The process of any one of claims 21 - 27 , wherein the heating is to greater than 1325° C.

30 . The process of any one of claims 21 - 27 , wherein the heating is in an inert or reducing atmosphere, wherein the atmosphere H 2 and a member selected form the group consisting of He, N 2 , Ar or a combination thereof.

31 . The process of claim 30 , wherein the heating is in argon.

32 . The process of claim 30 , wherein the heating is in Ar, Ar/H 2 O 2 , N 2 .

33 . The process of claim 30 , wherein the heating is conducted in an oven, with a laser, a Rapid Thermal Processing instrument, (RTP),infrared radiation, UV radiation, or a flash lamp.

34 . The process of claim 30 , wherein the lithium-stuffed garnet is calcined lithium-stuffed garnet.

35 . The process of any one of claims 21 - 30 , wherein the lithium-stuffed garnet is a sintered lithium-stuffed garnet.

36 . The process of any one of claims 21 - 30 , the lithium-stuffed garnet is an annealed lithium-stuffed garnet.

37 . The process of any one of claims 21 - 30 , the lithium-stuffed garnet is an annealed lithium-stuffed garnet consisting essentially of lithium-stuffed garnet.

38 . A process for making a solid electrolyte, comprising
a. providing lithium-stuffed garnet chemical precursors or calcined lithium-stuffed garnet, wherein the lithium-stuffed garnet chemical precursors or calcined lithium-stuffed garnet are provided having a narrow particle size distribution; b. shaping the lithium-stuffed garnet chemical precursors or calcined lithium-stuffed garnet into a thin film form factor; and c. sintering the lithium-stuffed garnet chemical precursors or calcined lithium-stuffed garnet using spark plasma sintering (SPS) or hot-press sintering (HPS) to provide a sintered lithium-stuffed garnet thin film.

39 . The method of claim 38 , wherein the particle size distribution has a d 90 less than 25-45 μm.

40 . The method of claim 38 , wherein the particle size distribution has a d 90 less than 2-20 μm.

41 . The method of claim 38 , wherein the particle size distribution has a d 90 of about 2-20 μm.

42 . The method of any one of claims 38 to 41 , wherein the sintering is SPS.

43 . The method of any one of claims 38 to 41 , wherein the sintering is hot-press sintering.

44 . The method of any one of claims 38 to 43 , further comprising polishing the sintered lithium-stuffed garnet thin film.

45 . The method of any one of claims 38 to 43 , further

Assignees

• Quantumscape Corp

Inventors

• Cao David
• Chao Cheng-Chieh
• Chen Zhebo
• Cheng Lei
• Donnelly Niall
• Hermann Wes
• Holme Tim
• Huang Tommy
• Kerman Kian
• Li Yang
• Maheshwari Harsh

Classifications

• H01M10/4235 Primary

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• C04B2235/3839

  Refractory metal carbides · CPC title

• C04B2235/5463

  Particle size distributions · CPC title

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title

• C04B2235/5436

  micrometer sized, i.e. from 1 to 100 micron · CPC title