# US 12,191,447 B2 · Gel electrolyte composition for a battery and a method of implementation > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,191,447 B2 - Document ID: US12191447B2 - Status: Granted - Kind: B2 - Application number: 18/443,716 - Filed: 2024-02-16 - Published: 2024-08-22 - Granted: 2025-01-07 - Earliest claimed: 2023-02-16 - Assignees: Anthro Energy, Inc. - Applicants: Anthro Energy, Inc. - Inventors: David George Mackanic; Joseph K. Papp - Web page: https://patentgrep.com/patent/US12191447B2 ## CPC - H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type - H01M 4/622: {being polymers} - H01M 4/625: {Carbon or graphite} - H01M 10/052: Li-accumulators - H01M 10/0567: characterised by the additives - H01M 2004/027: {Negative electrodes} - H01M 2004/028: {Positive electrodes} - H01M 2300/0082: Organic polymers - H01M 2300/0085: Immobilising or gelification of electrolyte - Y02E 60/10: Energy storage using batteries - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract A method can include: receiving a gel electrolyte precursor solution comprising a polymeric precursor (such as monomers or oligomers), an initiator, and a plasticizer; adding the gel electrolyte precursor solution to a battery stack; wetting the battery stack with the gel electrolyte precursor solution; and curing the gel electrolyte precursor to form a covalently bonded gel electrolyte network interspersed throughout the battery stack. ## Claims ### Claim 1 A method for forming a gel electrolyte battery comprising: receiving a first gel precursor solution comprising a plasticizer and a polymer precursor; receiving a second gel precursor solution comprising a solvent and a polymerization initiator; mixing the first gel precursor solution and the second gel precursor solution to form a gel electrolyte precursor with a viscosity between 10 and 50 centipoise; immediately after mixing, adding the gel electrolyte precursor to a battery; wetting a cathode, an anode, and a separator of the battery with the electrolyte precursor via pulsed vacuum wetting, wherein a vacuum pressure during each vacuum pulse is at most 0.95 Bar; at least 6 hours after wetting the cathode, the anode, and the separator of the battery; curing the gel electrolyte precursor by: fixing the battery with a force between 5-1000 psi; and heating the gel electrolyte precursor to a temperature between 60-80° C. for between 30 minutes and 24 hours; wherein after curing the gel electrolyte precursor forms a gel electrolyte throughout the cathode, the anode, and the separator. ### Claim 2 (depends on 1) The method of claim 1, further comprising before wetting the cathode, the anode, and the separator, tap charging the battery to between 1.5 and 2.2 V. ### Claim 3 (depends on 1) The method of claim 1, further comprising before curing the gel electrolyte cycling the battery to form a solid electrolyte interface (SEI) layer. ### Claim 4 (depends on 1) The method of claim 1, wherein the polymer precursor comprises a urethane acrylate or a urethane methacrylate oligomer. ### Claim 5 (depends on 1) The method of claim 1, wherein the plasticizer comprises: a polar aprotic solvent comprising at least one of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, vinylene carbonate, trimethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, trifluoropropylene carbonate, methylene ethylene carbonate, dioxazolone, hexahydroxybenzene triscarbonate, ethylenetetracarboxylic dianhydride, lactic acid O-carboxyanhydride, tetrahydroxy-1,4-benzoquinone biscarbonate, di-tert-butyl carbonate, di-tert-butyl decarbonate, diethyl carbonate, diethyl pyrocarbonate, dimethyl carbonate, ethyl methyl carbonate, diallyl carbonate, diphenyl carbonate, methyl(2,2,2-trifluoroethyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, dimethoxyethane, diethyl ether, tetrahydrofuran (oxolane), tetraethoxymethane, tetramethoxymethane, triethyl orthoacetate, triethyl orthoformate, trimethylorthoformate, 2,2-diethoxytetrahydrofuran, methyl formate, ethyl formate, methyl propionate, methyl butanoate, ethyl formate, ethyl acetate, ethyl propionate, propyl formate, propyl acetate, or propyl proprionate; and a salt comprising at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium chlorate, lithium 2,3,7,8-tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4.4]nonan-5-uide, lithium difluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide, lithium fluoromalonato(difluoro)borate, lithium trifluoromethanesulfonate, lithium tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4,4]nonan-5-uide, lithium trifluoro[(trifluoromethansulfonylazanidyl)sulfonyl]methane, lithium nitrate, or lithium 2,2-difluoro-4,5-dioxo-1,3,2-dioxaborolane-2-uide. ### Claim 6 (depends on 5) The method of claim 5, wherein the solvent in the step of receiving a second gel precursor solution is the polar aprotic solvent. ### Claim 7 A method comprising: receiving a gel electrolyte precursor solution comprising: an acrylate oligomer or a methacrylate oligomer comprising a toughening region; an initiator; and a plasticizer; adding the gel electrolyte precursor solution to a battery stack comprising a cathode, an anode, and a separator; wetting the battery stack with the gel electrolyte precursor solution; prior to or during wetting the battery stack, tap charging the battery stack to a voltage between 1.5 and 2.2 V; and curing the gel electrolyte precursor solution to form a covalently bonded gel electrolyte network interspersed throughout the cathode, the anode, and the separator. ### Claim 8 (depends on 7) The method of claim 7, wherein a viscosity of the gel electrolyte precursor is at most 50 cP at 25° C. ### Claim 9 (depends on 7) The method of claim 7, wherein the covalently bonded gel electrolyte network has an ionic conductivity of at least 0.1 mS/cm at 25° C. ### Claim 10 (depends on 7) The method of claim 7, wherein the plasticizer comprises: a polar aprotic solvent comprising at least one of ethylene carbonate, propylene carbonate, trimethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, trifluoropropylene carbonate, dioxazolone, hexahydroxybenzene triscarbonate, ethylenetetracarboxylic dianhydride, lactic acid O-carboxyanhydride, tetrahydroxy-1,4-benzoquinone biscarbonate, di-tert-butyl carbonate, di-tert-butyl decarbonate, diethyl carbonate, diethyl pyrocarbonate, dimethyl carbonate, ethyl methyl carbonate, diallyl carbonate, diphenyl carbonate, methyl(2,2,2-trifluoroethyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, dimethoxyethane, diethyl ether, tetrahydrofuran (oxolane), tetraethoxymethane, tetramethoxymethane, triethyl orthoacetate, triethyl orthoformate, trimethyl orthoformate, 2,2-diethoxytetrahydrofuran, methyl formate, ethyl formate, methyl propionate, methyl butanoate, ethyl formate, ethyl acetate, ethyl propionate, propyl formate, propyl acetate, or propyl propionate; and a salt comprising at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium chlorate, lithium 2,3,7,8-tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4.4]nonan-5-uide, lithium difluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide, lithium fluoromalonato(difluoro)borate, lithium trifluoromethanesulfonate, lithium tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4,4]nonan-5-uide, lithium trifluoro[(trifluoromethansulfonylazanidyl)sulfonyl]methane, lithium nitrate, or lithium 2,2-difluoro-4,5-dioxo-1,3,2-dioxaborolane-2-uide. ### Claim 11 (depends on 10) The method of claim 10, wherein the plasticizer further comprises an additive comprising at least one of fluoroethylene carbonate, vinylene carbonate, methylene ethylene carbonate, 3-fluoro-1,3-propanesultone, prop-1-ene-1,3-sultone, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tris(2,2,2-trifluorethyl) phosphate, bis(2,2,2-trifluoroethyl) methyl phosphate, trimethylphosphite, triethyl phosphite, tributyl phosphite, tris(2,2,2-trifluorethyl) phosphite, dimethyl methylphosphonate, diethyl ethylphosphonate, bis(2,2,2-trifluoroethyl) methylphosphonate, bis(2,2,2-trifluoroethyl) ethylphosphonate, hexamethoxycyclotriphosphazene, N-methyl-2-pyrrolidone, ethoxy(pentafluoro)cyclotriphosphazene, pentafluoro(phenoxy)cyclotriphosphazene, tris(trimethylsilyl)phosphite, tris(trimethylsilyl)phosphate, or diethyl phenylphosphonite. ### Claim 12 (depends on 7) The method of claim 7, wherein receiving a gel electrolyte precursor comprises mixing a first solution comprising the plasticizer and the acrylate oligomer or the methacrylate oligomer with a second solution comprising the initiator and a solvent. ### Claim 13 (depends on 12) The method of claim 12, wherein the first solution and the second solution are mixed immediately before adding the gel electrolyte precursor solution to the battery stack. ### Claim 14 (depends on 12) The method of claim 12, wherein the plasticizer comprises the solvent. ### Claim 15 (depends on 7) The method of claim 7, wherein curing the gel electrolyte precursor comprises thermally curing the gel electrolyte precursor by maintaining a temperature of the gel electrolyte precursor and the battery stack between 6° and 80° C. for between 0.5 and 24 hours. ### Claim 16 (depends on 15) The method of claim 15, wherein curing the gel electrolyte precursor comprises mechanically fixing the gel electrolyte precursor and the battery stack with a pressure between 5 psi and 1000 psi. ### Claim 17 (depends on 7) The method of claim 7, wherein the toughening region comprises a functional group capable of dynamic bonding via hydrogen bonding or ion pairing interactions. ### Claim 18 (depends on 7) The method of claim 7, wherein the covalently bonded gel electrolyte network further comprises at least one functional group that forms an ionic transport network. ### Claim 19 (depends on 18) The method of claim 18, wherein the at least one functional group comprises at least one functional group selected from: carbonate, ester, ketone, carbamide, carbamate, thiocarbamate, thiocarbamide, thiocarbonate, dithiocarbonate, ether, thioether, imide, imine, epoxide, amide, acid anhydride, nitrile, amidine, cyanate, isocyanate, nitrosooxy, nitro, nitroso, oxime, sulfinyl, sulfonyl, sulfonate ester, sulfone, thiocyanate, isothiocyanate, thioester, or dithiocarboxylic acid ester within a backbone of the acrylate oligomer or the methacrylate oligomer. ### Claim 20 (depends on 7) The method of claim 7, wherein wetting the battery stack comprises applying a plurality of vacuum pulses to the battery stack, wherein each vacuum pulse of the plurality of vacuum pulses comprises a pressure of at most about 0.95 Bar. ### Claim 21 (depends on 7) The method of claim 7, wherein wetting the battery stack further comprises aging the battery stack for up to 48 hours before curing the gel electrolyte precursor. ### Claim 22 A method comprising: receiving a gel electrolyte precursor solution comprising: an acrylate oligomer or a methacrylate oligomer comprising a toughening region; an initiator; and a plasticizer; adding the gel electrolyte precursor solution to a battery stack comprising a cathode, an anode, and a separator; wetting the battery stack with the gel electrolyte precursor solution; and thermally curing the gel electrolyte precursor solution to form a covalently bonded gel electrolyte network interspersed throughout the cathode, the anode, and the separator by maintaining a temperature of the gel electrolyte precursor and the battery stack between 6° and 80° C. for between 0.5 and 24 hours and mechanically fixing the gel electrolyte precursor and the battery stack with a pressure between 5 psi and 1000 psi. ### Claim 23 (depends on 22) The method of claim 22, wherein the plasticizer comprises: a polar aprotic solvent comprising at least one of ethylene carbonate, propylene carbonate, trimethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, trifluoropropylene carbonate, dioxazolone, hexahydroxybenzene triscarbonate, ethylenetetracarboxylic dianhydride, lactic acid O-carboxyanhydride, tetrahydroxy-1,4-benzoquinone biscarbonate, di-tert-butyl carbonate, di-tert-butyl decarbonate, diethyl carbonate, diethyl pyrocarbonate, dimethyl carbonate, ethyl methyl carbonate, diallyl carbonate, diphenyl carbonate, methyl(2,2,2-trifluoroethyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, dimethoxyethane, diethyl ether, tetrahydrofuran (oxolane), tetraethoxymethane, tetramethoxymethane, triethyl orthoacetate, triethyl orthoformate, trimethyl orthoformate, 2,2-diethoxytetrahydrofuran, methyl formate, ethyl formate, methyl propionate, methyl butanoate, ethyl formate, ethyl acetate, ethyl propionate, propyl formate, propyl acetate, or propyl propionate; and a salt comprising at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium chlorate, lithium 2,3,7,8-tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4.4]nonan-5-uide, lithium difluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide, lithium fluoromalonato(difluoro)borate, lithium trifluoromethanesulfonate, lithium tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4,4]nonan-5-uide, lithium trifluoro[(trifluoromethansulfonylazanidyl)sulfonyl]methane, lithium nitrate, or lithium 2,2-difluoro-4,5-dioxo-1,3,2-dioxaborolane-2-uide. ### Claim 24 (depends on 22) The method of claim 22, wherein the toughening region comprises a functional group capable of dynamic bonding via hydrogen bonding or ion pairing interactions. ### Claim 25 (depends on 22) The method of claim 22, wherein the covalently bonded gel electrolyte network further comprises at least one functional group that forms an ionic transport network. ### Claim 26 (depends on 25) The method of claim 25, wherein the at least one functional group comprises at least one functional group selected from: carbonate, ester, ketone, carbamide, carbamate, thiocarbamate, thiocarbamide, thiocarbonate, dithiocarbonate, ether, thioether, imide, imine, epoxide, amide, acid anhydride, nitrile, amidine, cyanate, isocyanate, nitrosooxy, nitro, nitroso, oxime, sulfinyl, sulfonyl, sulfonate ester, sulfone, thiocyanate, isothiocyanate, thioester, or dithiocarboxylic acid ester within a backbone of the acrylate oligomer or the methacrylate oligomer. ### Claim 27 (depends on 22) The method of claim 22, wherein wetting the battery stack comprises applying a plurality of vacuum pulses to the battery stack, wherein each vacuum pulse of the plurality of vacuum pulses comprises a pressure of at most about 0.95 Bar. ### Claim 28 (depends on 22) The method of claim 22, wherein wetting the battery stack further comprises aging the battery stack for up to 48 hours before curing the gel electrolyte precursor.