Lithium-stuffed garnet thin films and pellets having an oxyfluorinated and/or fluorinated surface and methods of making and using the thin films and pellets

Patent metadata

Field	Value
Publication number	US-2024204245-A1
Application number	US-202318477484-A
Country	US
Kind code	A1
Filing date	Sep 28, 2023
Priority date	Nov 6, 2017
Publication date	Jun 20, 2024
Grant date	—

Abstract

Set forth herein are processes for making lithium-stuffed garnet oxides (e.g., Li 7 La 3 Zr 2 O 12 , also known as LLZO) that have passivated surfaces comprising a fluorinate and/or an oxyfluorinate species. These surfaces resist the formation of oxides, carbonates, hydroxides, peroxides, and organics that spontaneously form on LLZO surfaces under ambient conditions. Also set forth herein are new materials made by these processes.

First claim

1 .- 92 . (canceled)

93 . A process for making a sintered lithium-stuffed garnet thin film or pellet, comprising:
(1) providing a solution comprising a first salt and a solvent; (2) providing a sintered lithium-stuffed garnet thin film or pellet; (3) contacting at least one surface of the sintered lithium-stuffed garnet thin film or pellet with the solution; and (4) removing the solution from the at least one surface of the sintered lithium-stuffed garnet thin film or pellet.

94 . The process of claim 93 , wherein the solution further comprises a second salt.

95 . The process of claim 94 , wherein the first and second salt is independently selected from the group consisting of LiPF 6 , lithium bis(perfluoroethanesulfonyl)imide (LIBETI), bis(trifluoromethane)sulfonimide lithium salt (LiTFSI), LiBF 4 , LiAsF 6 , lithium bis(fluorosulfonyl)imide (LiFSI), and combinations thereof.

96 . The process of claim 94 , wherein the concentration of the first salt is about 0.5 M to about 1.5 M; or the concentration of the first salt or the second salt is about 0.5 to about 1.5 M.

97 . The process of claim 96 , wherein the concentration of the first salt is about 0.5 M.

98 . The process of claim 96 , wherein the concentration of the second salt is about 0.5 M to about 1.5 M.

99 . The process of claim 98 , wherein the concentration of the second salt is about 1.35 M.

100 . The process of claim 93 , wherein the solvent is selected from the group consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonate (EMC), propylmethyl carbonate, nitroethyl carbonate, propylene carbonate (PC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), 2,5-dioxahexanedioic acid dimethyl ester, tetrahydrofuran (THF), 7-butyrolactone (GBL), fluoroethylene carbonate (FEC), fluoromethyl ethylene carbonate (FMEC), trifluoroethyl methyl carbonate (F-EMC), fluorinated 3-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoropropane/1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane (F-EPE), fluorinated cyclic carbonate (F-AEC), dioxolane, prop-1-ene-1,3-sultone (PES), sulfolane, acetonitrile (ACN), succinonitrile (SCN), pimelonitrile, suberonitrile, propionitrile, propanedinitrile, glutaronitrile (GLN), adiponitrile (ADN), hexanedinitrile, pentanedinitrile, acetophenone, isophorone, benzonitrile, ethyl propionate, methyl propionate, methylene methanedisulfonate, dimethyl sulfate, dimethyl sulfoxide (DMSO), ethyl acetate, methyl butyrate, dimethyl ether (DME), diethyl ether, dioxolane, gamma butyl-lactone, methyl benzoate, 2-methyl-5-oxooxolane-2-carbonitrile, and combinations thereof.

101 . The process of claim 100 , wherein the solvent is selected from the group consisting of succinonitrile (SCN), glutaronitile (GLN), sulfolane, ethylene carbonate (EC), ethyl-methyl carbonate (EMC), and combinations thereof.

102 . The process of claim 101 , wherein the solvent has a water content less than 200 ppm, or less than 150 ppm, or less than 100 ppm, or less than 60 ppm, or less than 50 ppm, or less than 40 ppm, or less than 30 ppm, or less than 20 ppm, or less than 10 ppm.

103 . The process of claim 93 , wherein the lithium-stuffed garnet thin film or pellet comprises 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.

104 . The process of claim 93 , wherein (3) is performed at a temperature between, or equal to, 0° C. and 60° C.

105 . The process of claim 93 , wherein (3) is performed at room temperature.

106 . The process of claim 95 , wherein the at least one surface of the lithium-stuffed garnet thin film or pellet, after (4), has a fluorinated surface.

107 . The process of claim 106 , wherein the at least one surface of the lithium-stuffed garnet thin film or pellet, after (4), has fluorine or fluoride present at a depth of penetration ranging from about 0.5 m to about 1.5 m.

108 . The process of claim 106 , wherein the at least one surface of the lithium-stuffed garnet thin film or pellet, after (4), comprises fluorine bonded to one or more elements in the lithium-stuffed garnet.

109 . The process of claim 93 , wherein the at least one surface is free or substantially free of a contaminant after (3).

110 . The process of claim 109 , wherein the contaminant is Li 2 CO 3 and the at least one surface has Li 2 CO 3 on the surface in an amount less than 1 atomic % as measured by XPS.

Assignees

• Quantumscape Battery Inc

Inventors

• Chao Cheng-Chieh
• Cheng Lei
• Dekmezian Christopher
• Ho Tiffany
• Holme Timothy
• Huang Tommy
• Mehrotra Amal
• Yang Aram

Classifications

• H01M2300/0074

  Ion conductive at high temperature · CPC title

• H01M10/0585

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• H01M10/0525

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

• C09C1/407

  Aluminium oxides or hydroxides · CPC title

• C01P2006/82

  water content · CPC title