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-2024006667-A1
Application number	US-202318348981-A
Country	US
Kind code	A1
Filing date	Jul 7, 2023
Priority date	Oct 21, 2016
Publication date	Jan 4, 2024
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 .- 49 . (canceled)

50 . A method for reducing the number of defects on a single layer sintered lithium-stuffed garnet thin film, the method comprising the following steps in the following order:
providing a single layer sintered lithium-stuffed garnet thin film in contact with a current collector layer in a first step; heating the surface of the sintered lithium-stuffed garnet thin film to 700° C. to 1200° C. for 1 hour to 10 hours in an inert or reducing atmosphere in a second step; wherein the inert or reducing atmosphere comprises a member selected from the group consisting of Ar, Ar/H 2 N 2 , or combinations thereof; and cooling the sintered lithium-stuffed garnet thin film in contact with a current collector layer in a third step in the inert or reducing atmosphere; wherein the current collector layer comprises a metal selected from Al, Cu, Ni, steel, or alloys thereof, or combinations thereof.

51 . The method of claim 50 , comprising heating the surfaces of the single layer sintered lithium-stuffed garnet thin film to at least 750° C.

52 . The method of claim 50 , comprising heating the surfaces of the single layer sintered lithium-stuffed garnet thin film to at least 900° C.

53 . The method of claim 50 , comprising heating the surfaces of the single layer sintered lithium-stuffed garnet thin film to at least 1000° C.

54 . The method of claim 50 , wherein the current collector comprises Ni.

55 . The method of claim 50 , wherein the single layer sintered lithium-stuffed garnet thin film has surfaces and a bulk therebetween, wherein the cooling in the third step is for a longest time which still provides for smaller grains on the surfaces than in the bulk.

56 . The method of claim 50 , wherein the single layer sintered lithium-stuffed garnet thin film has surfaces and a bulk therebetween, wherein the cooling in the third step is for a longest time which still provides for surfaces which is denser than the bulk.

57 . The method of claim 50 , wherein the single layer sintered lithium-stuffed garnet thin film has surfaces and a bulk therebetween, wherein the cooling in the third step is for a longest time which still provides for a surface which is less crystalline than the bulk.

58 . The method of claim 50 , wherein the heating in the second step is in an inert or reducing atmosphere.

59 . The method of claim 50 , wherein the inert or reducing atmosphere is Ar, Ar/H 2 , or N 2 .

60 . The method of claim 50 , wherein the heating in the second step is via an oven, a laser, a Rapid Thermal Processing instrument (RTP), infrared radiation, UV radiation, or a flash lamp.

61 . The method of claim 50 , wherein the single layer sintered lithium-stuffed garnet thin film has the empirical formula Li a La b Zr c Al d Me″ e O f , wherein 5<a<8.5; 2<b<4; 0<c≤2.5; 0≤d<2; 0≤e<2, and 10<f<13, and Me″ is a metal selected from Nb, Ga, or Ta.

62 . The method of claim 50 , wherein the single layer sintered lithium-stuffed garnet thin film has the empirical formula Li x La y Zr z O t ·qAl 2 O 3 , wherein 4<x<10, 1<y<4, 1<z<3, 6<t<14, and 0≤q≤1.

63 . The method of claim 50 , wherein the single layer sintered lithium-stuffed garnet thin film has surfaces and a bulk therebetween, wherein after heating the surfaces of the single layer sintered lithium-stuffed garnet thin film, the surfaces of the single layer sintered lithium-stuffed garnet thin film has a lower surface defect density than does the bulk.

64 . The method of claim 50 , wherein the single layer sintered lithium-stuffed garnet thin film has surfaces and a bulk therebetween, wherein after heating the surfaces of the single layer sintered lithium-stuffed garnet thin film, the surface is more dense than the bulk.

65 . The method of claim 50 , wherein the thickness of the single layer sintered lithium-stuffed garnet thin film is between 1 μm and 100 μm.

66 . The method of claim 50 , wherein prior to the heating the surfaces of the sintered lithium-stuffed garnet thin film to at least 400° C. in the second step, the sintered lithium-stuffed garnet thin film is comprised of a plurality of particles, wherein a particle size distribution of the particles has a d 90 of about 25-45 μm.

67 . The method of claim 50 , comprising heating the surfaces of the sintered lithium-stuffed garnet thin film to 700° C., 800° C., 900° C., 1000° C., 1100° C., or 1200° C., for 1 hour to 10 hours.

Assignees

• Quantumscape Battery Inc

Inventors

• Cao David
• Chao Cheng-Chieh
• Chen Zhebo
• Cheng Lei
• Donnelly Niall
• Hermann Wes
• Holme Timothy
• 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

• H01M10/0562

  Solid materials · CPC title

• C04B35/495

  based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates · CPC title

• C04B35/486 Primary

  Fine ceramics · CPC title

• C04B35/62218

  obtaining ceramic films, e.g. by using temporary supports · CPC title