# US 11,444,330 B2 · Electrolytic solution and electrochemical device using the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,444,330 B2 - Document ID: US11444330B2 - Status: Granted - Kind: B2 - Application number: 16/652,593 - Filed: 2020-03-30 - Published: 2021-12-30 - Granted: 2022-09-13 - Earliest claimed: 2019-05-23 - Assignees: Ningde Amperex Technology Limited - Applicants: Ningde Amperex Technology Limited - Inventors: Qian Wen; Bin Wang; Xiexue Peng; Jianming Zheng - Web page: https://patentgrep.com/patent/US11444330B2 ## CPC - H01M 10/052: Li-accumulators - H01M 10/0569: characterised by the solvents - H01M 4/382: {Lithium (H01M4/405 takes precedence)} - H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries - H01M 10/0567: characterised by the additives - H01M 4/134: Electrodes based on metals, Si or alloys - H01M 2300/0034: Fluorinated solvents - H01M 2300/004: Three solvents - 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 The present application relates to an electrolytic solution and an electrochemical device using the same. The electrolytic solution comprises a cyclic fluorocarbonate, a chain fluorocarbonate and a fluoroether compound, wherein based on the weight of the electrolytic solution, the weight percentage of the cyclic fluorocarbonate is 15 wt % to 80 wt %. The electrolytic solution provided by the present application has high electric conductivity and good electrochemical stability and safety performance, can significantly improve the cycle performance of the battery, and especially meet the demand for long cycle life of a lithium metal battery, and has a very large application value in the lithium metal battery. ## Claims ### Claim 1 An electrolytic solution comprising a cyclic fluorocarbonate, a chain fluorocarbonate and a fluoroether compound, wherein based on the weight of the electrolytic solution, the weight percentage of the cyclic fluorocarbonate is X, and the sum of the weight percentages of the chain fluorocarbonate and the fluoroether compound is Y, wherein X is 15 wt % to 80 wt %, and 0.67≤Y/X≤5.7. ### Claim 2 (depends on 1) The electrolytic solution according to claim 1, wherein based on the weight of the electrolytic solution, the weight percentage of the chain fluorocarbonate is 5 wt % to 70 wt %, and the weight percentage of the fluoroether compound is 5 wt % to 70 wt %. ### Claim 3 (depends on 1) The electrolytic solution according to claim 1, wherein the cyclic fluorocarbonate comprises the compound of Formula I, and the chain fluorocarbonate comprises the compound of Formula II: wherein R1, R2, R3 and R4 are each independently selected from hydrogen, a fluorine atom, an alkyl group having 1-12 carbon atoms, a fluoroalkyl group having 1-12 carbon atoms, a cycloalkyl group having 3-12 carbon atoms, a fluorocycloalkyl group having 3-12 carbon atoms, an alkenyl group having 2-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms, a heterocyclic group having 3-12 carbon atoms or a fluoroheterocyclic group having 3-12 carbon atoms, and wherein at least one of R1, R2, R3 and R4 is a fluorine atom, a fluoroalkyl group having 1-12 carbon atoms, a fluorocycloalkyl group having 3-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms or a fluoroheterocyclic group having 3-12 carbon atoms; wherein R5 and R6 are each independently selected from hydrogen , a fluorine atom, an alkyl group having 1-12 carbon atoms, a fluoroalkyl group having 1-12 carbon atoms, an alkoxy group having 1-12 carbon atoms, a fluoroalkoxy group having 1-12 carbon atoms, an alkenyl group having 2-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms, an aryl group having 6-26 carbon atoms or a fluoroaryl group having 6-26 carbon atoms, and at least one of R5 and R6 is a fluoroalkyl group having 1-12 carbon atoms, a fluoroalkoxy group having 1-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms or a fluoroaryl group having 6-26 carbon atoms. ### Claim 4 (depends on 1) The electrolytic solution according to claim 1, wherein the cyclic fluorocarbonate comprises at least one of the following compounds: fluoroethylene carbonate, 4,5-difluoroethylene carbonate or 4,4,5,5-tetrafluoroethylene carbonate; and the chain fluorocarbonate comprises at least one of the following compounds: methyl trifluoroethyl carbonate, methyl 2,2,3,3-tetrafluoropropyl carbonate or bis(2,2,2-trifluoroethyl) carbonate. ### Claim 5 (depends on 1) The electrolytic solution according to claim 1, wherein the fluoroether compound comprises at least one of the compounds of Formula III, Formula IV, Formula V or Formula VI: Rf1-O—Rf2 Formula III, Rf1-O—R Formula IV, Rf1-O—(R′—O)n—Rf2 Formula V, Rf1-O—(R′—O)n—R Formula VI, wherein in Formulas III, IV, V and VI, Rf1 and Rf2 are each independently selected from a linear or branched fluoroalkyl group having 1-12 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, R is a linear or branched alkyl group having 1-12 carbon atoms, R′ is a linear or branched alkylene group having 1-5 carbon atoms, and n is an integer from 1 to 5. ### Claim 6 (depends on 1) The electrolytic solution according to claim 1, wherein the fluoroether compound comprises at least one of the following compounds: CF3CH2OCH2CF3, HCF2CF2OCH2CF3, HCF2CF2OCH2CF2CF2H, (CF3)2CFCF(CF2CF3)(OCH3), CF3CHFCF2CH(CH3)OCF2CHFCF3, HCF2CF2CH2OCF2CF2CF2CF2H, HCF2CF2OCH2CF3, HCF2CF2OCH2CH2OCF2CF2H, HCF2CF2OCH2CH2CH2OCF2CF2H, HCF2CF2CH2OCF2CF2CF2H, HCF2CF2OCH2CH2OCF2CF2CF2H, HCF2CF2OCH2CH2CH2OCF2CF2CF2H, CH3OCH2CH2OCH2CH2F, CH3OCH2CH2OCH2CF3, CH3OCH2CH(CH3)OCH2CH2F, CH3OCH2CH(CH3)OCH2CF3, FCH2CH2OCH2CH2OCH2CH2F, FCH2CH2OCH2CH(CH3)OCH2CH2F, CF3CH2O(CH2CH2O)2CH2CF3 or CF3CH2OCH2CH(CH3)OCH2CF3. ### Claim 7 (depends on 1) The electrolytic solution according to claim 1, wherein the electrolytic solution further comprises an additive, the additive comprising at least one of the following compounds: vinylethylene carbonate, lithium bis(oxalate)borate, lithium borate difluoroxalate , lithium tetrafluoroborate, methylene methanedisulfonate, ethylene 4-trifluoromethyl carbonate, 1,3,2-dioxathiolane-2,2-dioxide, fluoroethylene carbonate, ethylene sulfite, vinylene carbonate, butanedioic anhydride, propylene sulfite, propenyl 1,3-sultone, bis(trimethylsilyl) sulfate, lithium nitrate, N-butyl,methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide, n-propyl, methylpiperidinium bis((trifluoromethyl)sulfonyl)imide, 1,3-dioxane, 1,4-dioxane, 1,2-bis(cyanoethoxy)ethane, adiponitrile, fumaronitrile, succinonitrile, 1,3,5-pentanetricarbonitrile, 1,3,6-hexanetricarbonitrile, 1,2,3-tris(2-cyanoethoxy)propane or a fluoroacylhydroxylamine compound, wherein the fluoroacylhydroxylamine compound comprises the compound of Formula VII: wherein R9 and R10 are each independently selected from a hydrocarbyl group having 1-12 carbon atoms or a fluorohydrocarbyl group having 1-12 carbon atoms, R11 is selected from a hydrogen atom or a hydrocarbyl group having 1-6 carbon atoms, and at least one of R9 and R10 is a fluorohydrocarbyl group having 1-12 carbon atoms. ### Claim 8 (depends on 7) The electrolytic solution according to claim 7, wherein the fluoroacylhydroxylamine compound comprises N,O-bis(trifluoroacetyl)hydroxylamine, N-methoxy-N-methyl-2,2,2-trifluoroacetamide or a combination thereof. ### Claim 9 (depends on 7) The electrolytic solution according to claim 7, wherein based on the weight of the electrolytic solution, the weight percentage of the additive is 0.05 wt % to 15 wt %. ### Claim 10 An electrochemical device, comprising an electrolytic solution, wherein the electrolytic solution comprises a cyclic fluorocarbonate, a chain fluorocarbonate and a fluoroether compound, wherein based on the weight of the electrolytic solution, the weight percentage of the cyclic fluorocarbonate is X, and the sum of the weight percentages of the chain fluorocarbonate and the fluoroether compound is Y, wherein X is 15 wt % to 80 w t%, and 0.67≤Y/X≤5.7. ### Claim 11 (depends on 10) The electrochemical device according to claim 10, wherein based on the weight of the electrolytic solution, the weight percentage of the chain fluorocarbonate is 5 wt % to 70 wt %, and the weight percentage of the fluoroether compound is 5 wt % to 70 wt %. ### Claim 12 (depends on 10) The electrochemical device according to claim 10, wherein the cyclic fluorocarbonate comprises the compound of Formula I, and the chain fluorocarbonate comprises the compound of Formula II: wherein R1, R2, R3 and R4 are each independently selected from hydrogen, a fluorine atom, an alkyl group having 1-12 carbon atoms, a fluoroalkyl group having 1-12 carbon atoms, a cycloalkyl group having 3-12 carbon atoms, a fluorocycloalkyl group having 3-12 carbon atoms, an alkenyl group having 2-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms, a heterocyclic group having 3-12 carbon atoms or a fluoroheterocyclic group having 3-12 carbon atoms, and wherein at least one of R1, R2, R3 and R4 is a fluorine atom, a fluoroalkyl group having 1-12 carbon atoms, a fluorocycloalkyl group having 3-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms or a fluoroheterocyclic group having 3-12 carbon atoms; wherein R5 and R6 are each independently selected from hydrogen , a fluorine atom, an alkyl group having 1-12 carbon atoms, a fluoroalkyl group having 1-12 carbon atoms, an alkoxy group having 1-12 carbon atoms, a fluoroalkoxy group having 1-12 carbon atoms, an alkenyl group having 2-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms, an aryl group having 6-26 carbon atoms or a fluoroaryl group having 6-26 carbon atoms, and at least one of R5 and R6 is a fluoroalkyl group having 1-12 carbon atoms, a fluoroalkoxy group having 1-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms or a fluoroaryl group having 6-26 carbon atoms. ### Claim 13 (depends on 10) The electrochemical device according to claim 10, wherein the cyclic fluorocarbonate comprises at least one of the following compounds: fluoroethylene carbonate, 4,5-difluoroethylene carbonate or 4,4,5,5-tetrafluoroethylene carbonate; and the chain fluorocarbonate comprises at least one of the following compounds: methyl trifluoroethyl carbonate, methyl 2,2,3,3-tetrafluoropropyl carbonate or bis(2,2,2-trifluoroethyl) carbonate. ### Claim 14 An electronic device comprising an electrochemical device, wherein the electrochemical device comprises an electrolytic solution, wherein the electrolytic solution comprises a cyclic fluorocarbonate, a chain fluorocarbonate and a fluoroether compound, wherein based on the weight of the electrolytic solution, the weight percentage of the cyclic fluorocarbonate is X, and the sum of the weight percentages of the chain fluorocarbonate and the fluoroether compound is Y, wherein X is 15 wt % to 80 wt %, and 0.67≤Y/X≤5.7. ### Claim 15 (depends on 14) The electronic device of claim 14, wherein based on the weight of the electrolytic solution, the weight percentage of the chain fluorocarbonate is 5 wt % to 70 wt %, and the weight percentage of the fluoroether compound is 5 wt % to 70 wt %. ### Claim 16 (depends on 14) The electronic device of claim 14, wherein the cyclic fluorocarbonate comprises the compound of Formula I, and the chain fluorocarbonate comprises the compound of Formula II: wherein R1, R2, R3 and R4 are each independently selected from hydrogen, a fluorine atom, an alkyl group having 1-12 carbon atoms, a fluoroalkyl group having 1-12 carbon atoms, a cycloalkyl group having 3-12 carbon atoms, a fluorocycloalkyl group having 3-12 carbon atoms, an alkenyl group having 2-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms, a heterocyclic group having 3-12 carbon atoms or a fluoroheterocyclic group having 3-12 carbon atoms, and wherein at least one of R1, R2, R3 and R4 is a fluorine atom, a fluoroalkyl group having 1-12 carbon atoms, a fluorocycloalkyl group having 3-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms or a fluoroheterocyclic group having 3-12 carbon atoms; wherein R5 and R6 are each independently selected from hydrogen , a fluorine atom, an alkyl group having 1-12 carbon atoms, a fluoroalkyl group having 1-12 carbon atoms, an alkoxy group having 1-12 carbon atoms, a fluoroalkoxy group having 1-12 carbon atoms, an alkenyl group having 2-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms, an aryl group having 6-26 carbon atoms or a fluoroaryl group having 6-26 carbon atoms, and at least one of R5 and R6 is a fluoroalkyl group having 1-12 carbon atoms, a fluoroalkoxy group having 1-12 carbon atoms, a fluoroalkenyl group having 2-12 carbon atoms or a fluoroaryl group having 6-26 carbon atoms. ### Claim 17 (depends on 14) The electronic device of claim 14, wherein the cyclic fluorocarbonate comprises at least one of the following compounds: fluoroethylene carbonate, 4,5-difluoroethylene carbonate or 4,4,5,5-tetrafluoroethylene carbonate; and the chain fluorocarbonate comprises at least one of the following compounds: methyl trifluoroethyl carbonate, methyl 2,2,3,3-tetrafluoropropyl carbonate or bis(2,2,2-trifluoroethyl) carbonate. ### Claim 18 (depends on 1) The electrolytic solution according to claim 1, wherein the electrolytic solution further comprises an additive, the additive comprises at least one of the following compounds: wherein based on the weight of the electrolytic solution, the weight percentage of the additive is 0.05 wt %-15 wt %. ### Claim 19 (depends on 10) The electrochemical device according to claim 10, wherein the electrolytic solution further comprises an additive, the additive comprising at least one of the following compounds: vinylethylene carbonate, lithium bis(oxalate)borate, lithium borate difluoroxalate , lithium tetrafluoroborate, methylene methanedisulfonate, ethylene 4-trifluoromethyl carbonate, 1,3,2-dioxathiolane-2,2-dioxide, fluoroethylene carbonate, ethylene sulfite, vinylene carbonate, butanedioic anhydride, propylene sulfite, propenyl 1,3-sultone, bis(trimethylsilyl) sulfate, lithium nitrate, N-butyl,methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide, n-propyl,methylpiperidinium bis((trifluoromethyl)sulfonyl)imide, 1,3-dioxane, 1,4-dioxane, 1,2-bis(cyanoethoxy)ethane, adiponitrile, fumaronitrile, succinonitrile, 1,3,5-pentanetricarbonitrile, 1,3,6-hexanetricarbonitrile, 1,2,3-tris(2-cyanoethoxy)propane or a fluoroacylhydroxylamine compound, wherein the fluoroacylhydroxylamine compound comprises the compound of Formula VII: wherein R9 and R10 are each independently selected from a hydrocarbyl group having 1-12 carbon atoms or a fluorohydrocarbyl group having 1-12 carbon atoms, R11 is selected from a hydrogen atom or a hydrocarbyl group having 1-6 carbon atoms, and at least one of R9 and R10 is a fluorohydrocarbyl group having 1-12 carbon atoms; wherein based on the weight of the electrolytic solution, the weight percentage of the additive is 0.05 wt % to 15 wt %. ### Claim 20 (depends on 14) The electronic device of claim 14, wherein the electrolytic solution further comprises an additive, the additive comprising at least one of the following compounds: vinylethylene carbonate, lithium bis(oxalate)borate, lithium borate difluoroxalate, lithium tetrafluoroborate, methylene methanedisulfonate, ethylene 4-trifluoromethyl carbonate, 1,3,2-dioxathiolane-2,2-dioxide, fluoroethylene carbonate, ethylene sulfite, vinylene carbonate, butanedioic anhydride, propylene sulfite, propenyl 1,3-sultone, bis(trimethylsilyl) sulfate, lithium nitrate, N-butyl, methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide, n-propyl,methylpiperidinium bis((trifluoromethyl)sulfonyl)imide, 1,3-dioxane, 1,4-dioxane, 1,2-bis(cyanoethoxy)ethane, adiponitrile, fumaronitrile, succinonitrile, 1,3,5-pentanetricarbonitrile, 1,3,6-hexanetricarbonitrile, 1,2,3-tris(2-cyanoethoxy)propane or a fluoroacylhydroxylamine compound, wherein the fluoroacylhydroxylamine compound comprises the compound of Formula VII: wherein R9 and R10 are each independently selected from a hydrocarbyl group having 1-12 carbon atoms or a fluorohydrocarbyl group having 1-12 carbon atoms, R11 is selected from a hydrogen atom or a hydrocarbyl group having 1-6 carbon atoms, and at least one of R9 and R10 is a fluorohydrocarbyl group having 1-12 carbon atoms; wherein based on the weight of the electrolytic solution, the weight percentage of the additive is 0.05 wt % to 15 wt %.