EP3665737A1 - Lithium-salz-gemisch und verwendungen davon als batterieelektrolyt - Google Patents

Lithium-salz-gemisch und verwendungen davon als batterieelektrolyt

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Publication number
EP3665737A1
EP3665737A1 EP18758933.8A EP18758933A EP3665737A1 EP 3665737 A1 EP3665737 A1 EP 3665737A1 EP 18758933 A EP18758933 A EP 18758933A EP 3665737 A1 EP3665737 A1 EP 3665737A1
Authority
EP
European Patent Office
Prior art keywords
mol
lithium
carbonate
molar
imide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18758933.8A
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English (en)
French (fr)
Inventor
Grégory Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP3665737A1 publication Critical patent/EP3665737A1/de
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to a mixture of lithium salts, as well as its use as a battery electrolyte.
  • a lithium-ion battery or a Li-Suffre battery comprises at least one negative electrode (anode), a positive electrode (cathode), a separator and an electrolyte.
  • the electrolyte generally consists of a lithium salt dissolved in a solvent which is generally a mixture of organic carbonates, in order to have a good compromise between the viscosity and the dielectric constant. Additives can then be added to improve the stability of the electrolyte salts.
  • LiPF6 lithium hexafluorophosphate
  • HF hydrofluoric acid
  • the reaction of LiPF6 with the residual water thus affects the longevity of the battery and can cause safety problems, particularly in the context of the use of lithium-ion batteries in private vehicles.
  • Other salts have been developed, such as LiTFSI
  • lithium bis (trifluoromethanesulfonyl) imide lithium bis (trifluoromethanesulfonyl) imide
  • LiFSI lithium bis (fluorosulfonyl) imide
  • the present application relates to a mixture comprising (preferably consisting essentially of, and preferably consisting of):
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiTDI lithium 2-trifluoromethyl-4,5-dicyanoimidazolate
  • LiPFe lithium hexafluorophosphate
  • the mixture comprises (preferably consisting essentially of, and preferably consisting of):
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiPFe lithium hexafluorophosphate
  • the molar percentages are based on the total number of moles of the compounds present in the mixture.
  • lithium salt of bis (fluorosulfonyl) imide lithium bis (sulfonyl) imide
  • LiFSI lithium bis (fluorosulfonyl) imide
  • total number of moles of the compounds of the mixture corresponds to the sum of the number of moles of each compound present in the mixture.
  • LiTDI Lithium 2-trifluoromethyl-4,5-dicyanoimidazolate, known under the name LiTDI, has the following structure:
  • Impurities may be present in the mixtures, for example less than 3000 ppm, preferably less than 1000 ppm, in particular less than 500 ppm relative to the total weight of said mixture.
  • ppm or "part per million” means ppm by weight. Impurities may be present in each LiFSI, LiTDI or LiPF 6 salt, for example less than 3000 ppm, preferably less than 1000 ppm, in particular less than 500 ppm, for example less than 300 ppm by weight. relative to the total weight of each salt.
  • LiFSI can be obtained by any known method, for example by the method described in WO2015 / 158979, WO201 1/065502 or WO201 1/149095.
  • LiTDI can be obtained by any known method, for example by the method described in WO2013 / 072591 or WO2010 / 023413.
  • LiPF6 can be obtained by any known method, for example by the method described in US 3,607,020, US 3,907,977 or in JP60251 109.
  • the mixture according to the invention comprises:
  • LiFSI LiFSI
  • the content of LiFSI in the mixture according to the invention is chosen from one of the following molar percentages: from 1% to 99%, from 1% to 95%, from 5% to 90%, from 5% to 85%, 5% to 80%, 5% to 75%, 5% to 70%, 5% to 65%, 5% to 50%, 5% to 45%, 5% to % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% at 65%, from 10% to 60%, from 10% to 55%, from 10% to 50%, from 10% to 45%, from 15% to 99%, from 15% to 95%, from 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55% %, 15% to 50%, 15% to 45%, 20% to 99%, 20% to 95%, 20% to 90%, 20% to 85%, 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 99%,
  • the content of LiTDI in the mixture according to the invention is chosen from one of the following molar percentages: from 1% to 99%, from 1% to 95%, from 5% to 90%, from 5% to 85%, 5% to 80%, 5% to 75%, 5% to 70%, 5% to 65%, 5% to 50%, 5% to 45%, 5% to % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% at 65%, from 10% to 60%, from 10% to 55%, from 10% to 50%, from 10% to 45%, from 15% to 99%, from 15% to 95%, from 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55% %, 15% to 50%, 15% to 45%, 20% to 99%, 20% to 95%, 20% to 90%, 20% to 85%, 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 99%,
  • the content of LiPF 6 in the mixture according to the invention is chosen from one of the following molar percentages: from 1% to 99%, from 1% to 95%, from 5% to 90%, from 5% to 85%, 5% to 80%, 5% to 75%, 5% to 70%, 5% to 65%, 5% to 50%, 5% to 45%, 5% to % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% at 65%, from 10% to 60%, from 10% to 55%, from 10% to 50%, from 10% to 45%, from 15% to 99%, from 15% to 95%, from 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55% %, 15% to 50%, 15% to 45%, 20% to 99%, 20% to 95%, 20% to 90%, 20% to 85%, 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 99%,
  • the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
  • the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
  • the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
  • the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
  • the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
  • the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
  • the aforementioned mixture comprises (preferably consisting essentially of, and preferably consists of):
  • the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
  • the LiFSI content is greater than or equal to the LiTDI content, and / or the LiPF6 content is greater than or equal to LiTDI.
  • the molar ratio LiFSI / LiTDI / LiPF6 is included:
  • the molar ratio LiFSI / LiTDI / LiPF 6 is 4/3/3; between 1/1/1 and 1/10/1, preferably between 1/1/1 and 1/5/1, preferably between 1/1/1 and 1/2/1;
  • LiFSI / LiTDI / LiPF 6 is 5/2/3.
  • the LiFSI / LiPF6 molar ratio in the aforementioned mixture is between 1 and 10, preferably between 1 and 5, preferably between 1 and 2.
  • the molar ratio LiFSI / LiPF6 in the mixture is 4 / 3 or 5/3.
  • the present application also relates to the use of a mixture as defined above, in a battery, for example a Li-ion battery, in particular in a temperature range of between -30 ° C. and 65 ° C., preferentially between -25 ° C and 60 ° C, preferably at a temperature greater than or equal to 25 ° C, preferably between 25 ° C and 65 ° C, preferably between 40 ° C and 60 ° C.
  • the use is done in mobile devices, such as mobile phones, cameras, tablets or laptops, in electric vehicles, or in renewable energy storage.
  • the present invention also relates to an electrolyte composition, in particular for a Li-ion battery, comprising the mixture of lithium salts as defined above, at least one solvent, and optionally at least one electrolytic additive.
  • the electrolyte composition does not comprise any other alkali or alkaline earth salt than those of the aforementioned mixture.
  • the electrolyte composition does not comprise any other lithium salt than LiFSI, LiPF6 and LiTDI.
  • the electrolyte composition does not include LiTFSI.
  • the LiFSI, LiPF6 and LiTDI salts represent 100% of all the salts present in the composition.
  • electrospray composition In the context of the invention, “electrolyte composition”, “electrolyte” and “electrolyte composition” are used interchangeably.
  • the electrolyte composition comprises from 1% to 99% by weight of the aforementioned mixture, preferably from 5% to 99%, and advantageously from 20% to 95%, relative to the total mass of the composition.
  • the electrolyte composition comprises from 1% to 99% by weight of solvent, preferably from 5% to 99%, and advantageously from 20% to 95%, relative to the total mass of the composition.
  • the molar concentration of the aforementioned mixture in the electrolyte composition is less than or equal to 5 mol / L, advantageously less than or equal to 4 mol / L, preferably less than or equal to 2 mol / L, preferentially less than or equal to 1, 5 mol / L, and in particular less than or equal to 1, 1 mol / L, for example less than or equal to 1 mol / L.
  • the molar concentrations of LiFSI, LiTDI and LiPF6 in the electrolyte composition are such that:
  • the aforementioned electrolyte composition comprises:
  • the electrolyte composition according to the invention comprises: at least 0.05 mol / L, preferably at least 0.1 mol / L, preferably at least 0.15, even more preferably at least 0 2 mol / L, advantageously at least 0.25 mol / L, and still more advantageously at least 0.3 mol / L of LiFSI; and or
  • At least 0.05 mol / L preferably at least 0.1 mol / L, preferably at least 0.15, still more preferably at least 0.2 mol / L, advantageously at least 0.25 mol / L, and still more preferably at least 0.3 mol / L of LiTDI; and or
  • At least 0.05 mol / l preferably at least 0.1 mol / l, preferably at least 0.15, even more preferably at least 0.2 mol / l, advantageously at least 0.25 mol / l, and still more preferably at least 0.3 mol / L of LiPF6.
  • the molar concentration of LiFSI in the electrolyte composition is chosen from one of the following concentrations: from 0.01 to 0.99 mol / L, from 0.01 to 0.95 mol / L , from 0.05 to 0.90 mol / L, from 0.05 to 0.85 mol / L, from 0.05 to 0.80 mol / L, from 0.05 to 0.75 mol / L, from 0.05 to 0.70 mol / L, 0.05 to 0.65 mol / L, 0.05 to 0.50 mol / L, 0.05 to 0.45 mol / L, 0.1 at 0.99 mol / L, from 0.1 to 0.95 mol / L, from 0.1 to 0.90 mol / L, from 0.1 to 0.85 mol / L, from 0.1 to 0 , 80 mol / L, 0.1 to 0.75 mol / L, 0.1 to 0.70 mol / L, 0.1 to 0.65 mol / L, 0.1 to 0.50 mol / L, 0.1 to 0.
  • the molar concentration of LiTDI in the electrolyte composition is chosen from one of the following concentrations: from 0.01 to 0.99 mol / L, from 0.01 to 0.95 mol / L , from 0.05 to 0.90 mol / L, from 0.05 to 0.85 mol / L, from 0.05 to 0.80 mol / L, from 0.05 to 0.75 mol / L, from 0.05 to 0.70 mol / L, 0.05 to 0.65 mol / L, 0.05 to 0.50 mol / L, 0.05 to 0.45 mol / L, 0.1 at 0.99 mol / L, from 0.1 to 0.95 mol / L, from 0.1 to 0.90 mol / L, from 0.1 to 0.85 mol / L, from 0.1 to 0 , 80 mol / L, 0.1 to 0.75 mol / L, 0.1 to 0.70 mol / L, 0.1 to 0.65 mol / L, 0.1 to 0.50 mol / L, 0.1 to 0.
  • the molar concentration of LiPF6 in the electrolyte composition is chosen from one of the following concentrations: from 0.01 to 0.99 mol / L, from 0.01 to 0.95 mol / L , from 0.05 to 0.90 mol / L, from 0.05 to 0.85 mol / L, from 0.05 to 0.80 mol / L, from 0.05 to 0.75 mol / L, from 0.05 to 0.70 mol / L, 0.05 to 0.65 mol / L, 0.05 to 0.50 mol / L, 0.05 to 0.45 mol / L, 0.1 at 0.99 mol / L, from 0.1 to 0.95 mol / L, from 0.1 to 0.90 mol / L, from 0.1 to 0.85 mol / L, from 0.1 to 0 , 80 mol / L, 0.1 to 0.75 mol / L, 0.1 to 0.70 mol / L, 0.1 to 0.65 mol / L, 0.1 to 0.50 mol / L, 0.1 to 0.
  • the electrolyte composition comprises:
  • the electrolyte composition comprises:
  • the electrolyte composition comprises:
  • the electrolyte composition comprises:
  • the electrolyte composition comprises:
  • the electrolyte composition comprises
  • the electrolyte composition comprises:
  • the electrolyte composition comprises:
  • the above-mentioned electrolyte composition is such that:
  • the molar concentration of LiFSI is greater than or equal to 0.30 mol / L, and / or
  • the molar concentration of LiTDI is less than or equal to 0.40 mol / L;
  • the molar concentration of LiPF 6 is less than or equal to 0.50 mol / l.
  • the aforementioned electrolyte composition is such that the molar concentration of LiFSI is greater than or equal to the molar concentration of LiTDI, and / or the molar concentration of LiPF6 is greater than or equal to that of LiTDI.
  • the aforementioned electrolyte composition is such that the molar ratio LiFSI / LiPF 6 in said composition is between 1/1 and 10/1, preferably between 1/1 and 5/1, preferably between 1 / 1 and 2/1.
  • the molar ratio LiFSI / LiPFe in the mixture is 4/3 or 5/3.
  • the electrolyte composition may comprise a solvent or a mixture of solvents, such as for example two, three or four different solvents.
  • the solvent of the electrolyte composition may be a liquid solvent, optionally gelled with a polymer, or a polar polymer solvent optionally plasticized with a liquid.
  • the solvent is an organic solvent, preferably aprotic.
  • the solvent is a polar organic solvent.
  • the solvent is selected from the group consisting of ethers, carbonates, esters, ketones, partially hydrogenated hydrocarbons, nitriles, amides, alcohols, sulfoxides, sulfolane, nitromethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 3-methyl-2-oxazolidinone, and their mixtures.
  • ethers such as, for example, dimethoxyethane (DME), methyl ethers of oligoethylene glycols of 2 to 5 oxyethylene units, dioxolane, dioxane, dibutyl ether, tetrahydrofuran, and their mixtures.
  • DME dimethoxyethane
  • esters mention may be made of phosphoric acid esters or sulphite esters.
  • Mention may be made, for example, of methyl formate, methyl acetate, methyl propionate, ethyl acetate, butyl acetate, gamma butyrolactone or their mixtures.
  • ketones there may be mentioned cyclohexanone.
  • nitriles there may be mentioned for example acetonitrile, pyruvonitrile, propionitrile, methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methoxyglutaronitrile, 2 methylglutaronitrile, 3-methylglutaronitrile, adiponitrile, malononitrile, and mixtures thereof.
  • cyclic carbonates such as, for example, ethylene carbonate (EC) (CAS: 96-49-1), propylene carbonate (PC) (CAS: 108-32-7) , butylene carbonate (BC) (CAS: 4437-85-8), dimethyl carbonate (DMC) (CAS: 616-38-6), diethyl carbonate (DEC) (CAS: 105-58-8 ), methyl carbonate ethyl (EMC) (CAS: 623-53-0), diphenyl carbonate (CAS 102-09-0), methyl carbonate phenyl (CAS: 13509-27-8), carbonate of dipropyl (DPC) (CAS: 623-96-1), methyl carbonate and propyl (MPC) (CAS: 1333-41-1), ethyl carbonate and propyl carbonate (EPC), carbonate of vinylene (VC) (CAS: 872-36-6), fluoroethylene carbonate (FEC) (CAS: cyclic carbonates such as, for example, ethylene
  • the particularly preferred solvent is selected from carbonates and mixtures thereof.
  • the following mixtures may notably be mentioned: ethylene carbonate (EC) / propylene carbonate (PC) / dimethyl carbonate (DMC) in a weight ratio 1/1/1; ethylene carbonate (EC) / propylene carbonate (PC) / diethyl carbonate (DEC) in a weight ratio 1/1/1;
  • EC ethylene carbonate
  • EMC methyl ethyl carbonate
  • the solvent of the electrolyte composition is ethylene carbonate (EC) / methyl ethyl carbonate (EMC) in a volume ratio of 3/7.
  • the electrolyte composition comprises at least one electrolytic additive.
  • the electrolyte additive is selected from the group consisting of fluoroethylene carbonate (FEC), vinylene carbonate, 4-vinyl-1,3-dioxolan-2-one, pyridazine, vinyl pyridazine, quinoline, vinyl quinoline, butadiene, sebaconitrile, LiB (C20 4 ) 2, lithium nitrate, alkyldisulfide, fluorotoluene, 1,4-dimethoxytetrafluorotoluene, t-butylphenol, di-t -butylphenol, tris (pentafluorophenyl) borane, oximes, aliphatic epoxides, halogenated biphenyls, methacrylic acids, ethyl allyl carbonate, vinyl acetate, divinyl adipate, acrylonitrile , 2-vinylpyridine, maleic anhydride, methyl c
  • the content of electrolyte additive in the electrolyte composition is between 0.01% and 10%, preferably between 0.1% and 4% by weight relative to the total mass of the electrolyte composition.
  • the content of electrolytic additive in the electrolyte composition is less than or equal to 2% by weight relative to the total mass of the composition.
  • the content of electrolyte additive in the electrolyte composition may for example be between 0.01% and 10%, preferably between 0.1% and 4% by weight, relative to the total weight of the solvent of said composition.
  • the electrolyte composition according to the invention is chosen from one of the following compositions:
  • the electrolyte composition according to the invention is chosen from one of the following compositions:
  • the electrolyte composition may be prepared by any means known to those skilled in the art, for example by dissolving, preferably with stirring, salts in appropriate proportions of solvent (s) and / or additive (s). .
  • the present application also relates to the use of an electrolyte composition as defined above, in a Li-ion battery, in particular in a temperature range of between -30 ° C. and 65 ° C., preferably between -30 ° C. and 65 ° C. 25 ° C and 60 ° C, preferably at a temperature greater than or equal to 25 ° C, preferably between 25 ° C and 65 ° C, preferably between 40 ° C and 60 ° C.
  • the use is in mobile devices, for example mobile phones, cameras, tablets or laptops, in electric vehicles, or in the storage of renewable energy.
  • the present application also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and a mixture of lithium salts as described above.
  • the present application also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte composition as defined above, interposed between the negative electrode and the positive electrode.
  • the electrochemical cell may also comprise a separator, in which the electrolyte composition as defined above is impregnated.
  • the present invention also relates to a battery comprising at least one electrochemical cell as described above. When the battery comprises several electrochemical cells according to the invention, said cells can be assembled in series and / or in parallel.
  • the term "negative electrode" means the electrode which acts as anode, when the battery delivers current (that is to say when it is in the process of discharge) and which makes cathode office when the battery is charging process.
  • the negative electrode typically comprises an electrochemically active material, optionally an electronically conductive material, and optionally a binder.
  • electrochemically active material means a material capable of reversibly inserting ions.
  • the term "electronically conductive material” means a material capable of driving the electrons.
  • the negative electrode of the electrochemical cell comprises as electrochemically active material, graphite, lithium, a lithium alloy, a type lithium titanate LÎ4Ti 5 0 i2 or ⁇ 2, silicon or an alloy of lithium and silicon, a tin oxide, a lithium intermetallic compound, or a mixture thereof.
  • the negative electrode may comprise lithium, which may then consist of a metal lithium film or an alloy comprising lithium.
  • An example of a negative electrode may comprise a bright lithium film prepared by rolling between rolls of a lithium strip.
  • positive electrode means the electrode which acts as cathode, when the battery delivers current (that is to say when it is in the process of discharge) and which serves anode when the battery is charging.
  • the positive electrode typically comprises an electrochemically active material, optionally an electronically conductive material, and optionally a binder.
  • the material of the positive electrode may also include, in addition to the electrochemically active material, an electronically conductive material such as a carbon source, including, for example, carbon black, Ketjen ® carbon, Shawinigan carbon, graphite, graphene, carbon nanotubes, carbon fibers (such as gas-phase carbon fibers (VGCF), non-powdery carbon obtained by carbonization of an organic precursor, or a combination of two or more thereof
  • an electronically conductive material such as a carbon source, including, for example, carbon black, Ketjen ® carbon, Shawinigan carbon, graphite, graphene, carbon nanotubes, carbon fibers (such as gas-phase carbon fibers (VGCF), non-powdery carbon obtained by carbonization of an organic precursor, or a combination of two or more thereof
  • Other additives may also be present in the material of the positive electrode, such as lithium salts or inorganic particles of ceramic or glass type, or other compatible active materials (for example, sulfur).
  • the material of the positive electrode may also comprise a binder
  • binders include linear, branched and / or cross-linked polymeric polyether binders (e.g. s based on poly (ethylene oxide) (PEO), or poly (propylene oxide) (PPO) or a mixture of both (or a co-polymer EO / PO), and optionally comprising crosslinkable units ), water-soluble binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)) or fluoropolymer-type binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof.
  • PEO poly (ethylene oxide)
  • PPO poly (propylene oxide)
  • crosslinkable units e.g. s based on poly (
  • Some binders such as those soluble in water, may also include an additive such as CMC (carboxymethylcellulose).
  • CMC carboxymethylcellulose
  • the salt mixture according to the invention advantageously has good ionic conductivity in solution.
  • the salt mixture according to the invention advantageously makes it possible to improve the power performances of the battery, which makes it possible, for example, to recharge the battery more quickly, or to provide the necessary power in the event of a peak of energy.
  • the salt mixture according to the invention also advantageously allows to have good performance, especially in terms of power over a wide temperature range, for example cold, or over a temperature range of about -25 ° C. at about 60 ° C.
  • the salt mixture according to the invention advantageously allows a good compromise between good ionic conductivity in solution, a good lifetime, electrochemical stability, and power performance over a wide range of temperatures, such as for example - About 25 ° C to about 60 ° C.
  • "between x and y" or “between x and y” means an interval in which the terminals x and y are included.
  • the range “between 1% and 98%” or “ranging from 1% to 98%” includes in particular the values 1 and 98%.
  • EMC methyl carbonate ethyl (CAS 623-53-0)
  • FEC fluoroethylene carbonate
  • LiFF 6 BASF Corporation
  • the LiFSI used is obtained in particular by the process described in application WO2015 / 158979, while LiTDI is derived from the process described in patent application WO2013 / 072591.
  • composition 1 (according to the invention): 0.40M LiFSI, 0.30M LiTDI and 0.30M LiPF 6 , solvent mixture EC / EMC 3/7 (volume ratio), 2% by weight in FEC (relative to the total weight of the EC / EMC solvent mixture);
  • composition 2 (comparative): 0.40M LiTFSI, 0.30M LiTDI and 0.30M LiPF 6 , solvent mixture EC / EMC 3/7 (volume ratio), 2% by weight FEC (relative to the total weight) EC / EMC solvent mixture).
  • the compositions were prepared according to the following procedure: Composition 1:
  • the composition 1 comprises LiFSI, LiTDI, LiPF 6 , EC / EMC (3/7 ratio by volume), FEC (2% by weight relative to the weight of the solvent EC / EMC 3/7 volume), the total content of LiFSI in composition 1 being 0.40 mol / L, the total content of LiTDI in composition 1 being 0.30 mol / L, the total content of LiPF6 in the composition being 0.30 mol / L.
  • Composition 2 is a composition of Composition 2:
  • R is equal to the opposite of the ordinate at the origin divided by the directing coefficient of the equation of the linear regression.
  • composition 1 advantageously has a better ionic conductivity than the composition 2.
  • Example 2 Power test
  • the method involves increasing the discharge rate of a battery to observe the ability of the electrolyte to respond to the stress imposed by the electrical circuit.
  • Cathode LiNo.33 Mno.33Coo.33O2 (89%), VGCF carbon fiber (2.5%), carbon black (2.5%) and 6% Pvdf binder.
  • the current was varied between 2.7 and 4.2 V, with discharges operated in the following order: C / 20, C / 10, C / 5, C / 2, C and 2C.
  • composition 1 advantageously allows to work at higher power regimes than the composition 2.
  • These high speeds are particularly sought after in commercial batteries as part of nomadic devices that demand more power, and electric vehicles because of their low autonomy require fast recharges and therefore electrolytes to work at high speeds.

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EP18758933.8A 2017-08-07 2018-07-26 Lithium-salz-gemisch und verwendungen davon als batterieelektrolyt Pending EP3665737A1 (de)

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FR1757559A FR3069959B1 (fr) 2017-08-07 2017-08-07 Melange de sels de lithium et ses utilisations comme electrolyte de batterie
PCT/FR2018/051912 WO2019030440A1 (fr) 2017-08-07 2018-07-26 Melange de sels de lithium et ses utilisations comme electrolyte de batterie

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FR3096512B1 (fr) * 2019-05-22 2021-11-05 Arkema France Electrolyte a base de sels de lithium
FR3102010B1 (fr) * 2019-10-15 2022-06-03 Arkema France Procédé de régulation de la température d’une batterie comprenant un sel de lithium
CN111477957B (zh) * 2020-04-22 2021-04-16 浙江大学 一种含复合添加剂的锂金属电池电解液及其制备方法
KR102632922B1 (ko) * 2023-03-22 2024-02-05 주식회사 천보 저감된 리튬 플루오로설포네이트 포함 리튬 비스(플루오로설포닐)이미드의 카보네이트 용액 및 이를 포함하는 전해액

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JP2020529425A (ja) 2020-10-08
WO2019030440A1 (fr) 2019-02-14
FR3069959B1 (fr) 2019-08-23
FR3069959A1 (fr) 2019-02-08
CN110998950A (zh) 2020-04-10

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