EP3747076A2 - Mischung aus kalium- und lithiumsalzen und verwendung davon in einer batterie - Google Patents

Mischung aus kalium- und lithiumsalzen und verwendung davon in einer batterie

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Publication number
EP3747076A2
EP3747076A2 EP19709545.8A EP19709545A EP3747076A2 EP 3747076 A2 EP3747076 A2 EP 3747076A2 EP 19709545 A EP19709545 A EP 19709545A EP 3747076 A2 EP3747076 A2 EP 3747076A2
Authority
EP
European Patent Office
Prior art keywords
salt
formula
mixture
ppm
weight
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
EP19709545.8A
Other languages
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 EP3747076A2 publication Critical patent/EP3747076A2/de
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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
    • 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
    • H01M10/0568—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
    • H01M10/056—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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 and potassium salts, as well as its use in a battery.
  • a battery (such as for example 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.
  • the passivation layers formed during the first discharge charging cycles are essential for the life of the battery.
  • passivation layers there may be mentioned in particular the passivation layer on aluminum which is the current collector used at the cathode, or else the “Solid Electrolyte Interface” (SEI) which is the layer both inorganic and polymeric which is formed at the anode / electrolyte and cathode / electrolyte interface.
  • SEI Solid Electrolyte Interface
  • the formation of dendrites on a lithium metal anode also causes a decrease in battery life.
  • the present application relates to a mixture comprising (preferably consisting essentially of, and preferably consisting of):
  • Rf represents F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C 9 F 19; and their mixtures;
  • Rp is F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C 9 F 19; and their mixtures.
  • ppm or "part per million” means ppm by weight.
  • the present invention relates to a mixture comprising (preferably consisting essentially of, and preferably consisting of):
  • R 1 -SO 2 -NU-SO 2 -R 2 in which R 1 and R 2 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 11 , C 6 F 13 , C 7 F 15 , CeF 17, or C 9 F 19;
  • Rp is F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C4H4F5, C5F11, C6F13, C7F15, CeF, or C 9 F 19; and their mixtures.
  • the mixture comprises:
  • the mixture comprises from 1 to 1000 ppm of at least one aforementioned potassium salt B, preferably from 1 to 50 ppm, preferably from 1 to 20 ppm, and even more preferably from 1 to 10 ppm. .
  • the mixture comprises at least one lithium salt A as defined above, in a mass content greater than or equal to 99% by weight relative to the total weight of the mixture, preferably greater than or equal to 99 , 5%, preferentially greater than or equal to 99.9%, advantageously greater than or equal to 99.95%, still more preferably greater than or equal to 99.99%, still more advantageously greater than or equal to 99.995%, preferably higher or equal to 99.999%, for example greater than or equal to 99.9995% by weight relative to the total weight of the mixture.
  • the mixture comprises at least one potassium salt B as defined above, in a mass content of less than or equal to 10,000 ppm, preferably less than or equal to 5,000 ppm, preferably less than or equal to 1 000 ppm, advantageously less than or equal to 500 ppm, even more preferably less than or equal to 100 ppm, even more advantageously less than or equal to 50 ppm, advantageously less than or equal to 10 ppm, for example less than or equal to 5 ppm in weight relative to the total weight of the mixture.
  • the mixture comprises:
  • the mixture comprises at least one lithium salt A and at least one potassium salt B, said salts having the same anion.
  • the mixture preferably comprises at least one lithium salt A chosen from the group consisting of LiPF 6 , LiBF 4 , CH 3 COO, CH 3 SO 3 U, CF 3 SO 3 U, CF 3 COO, L 1. 2 B 12 F 12 , L 1BC 4 O 8 , and mixtures thereof, the lithium salt A being preferably L1PF 6 ; and at least one potassium salt B selected from the group consisting of KPF 6 , KBF 4 , CH 3 COOK, CH 3 SO 3 K, CF 3 SO 3 K, CF 3 COOK, K 2 B 12 F 12 , KBC 4 O 8, and mixtures thereof, the potassium salt B being preferably KPF 6 .
  • the mixture preferably comprises at least one lithium salt A chosen from the group consisting of LiPF 6 , L 1 BF 4 , CH 3 COOH, CH 3 SO 3 U, CF 3 SO 3 U, CF 3 COO, U 2 B 12 F 12 , UBC 4 O 8 , and mixtures thereof, the lithium salt A being preferably LiPF 6 ; and at least one potassium salt B having the formula (III) R 3 -SO 2 -NK-SO 2 -R 4 in which R 3 and R 4 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3, C 2 H 3 F 2 , C 2 F 5, C 3 F 7, C 3 H 2 F 5, C 3 H 4 F 3, C 4 F 9, C 4 H 2 F 7, C 4 H 4 F 5, C 5 F 11, C 6 F 13, C 7 F 15, CeF 7, or C 9 F 19 .
  • R 3 and R 4 preferably representing, independently of one another, F or CF 3 , and preferably F
  • the mixture preferably comprises at least one lithium salt A chosen from the group consisting of LiPF 6 , L 1 BF 4 , CH 3 COOH, CH 3 SO 3 U, CF 3 SO 3 U, CF 3 COO, U 2 B 12 F 12 , UBC 4 O 8 , and mixtures thereof, the lithium salt A being preferably LiPF 6 ; and at least one potassium salt B having the above-mentioned formula (IV) wherein Rp is F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 11 , C 6 F 13 , C 7 F 15, C 8 F 17, OR C 9 F 19, preferably Rp CF3.
  • LiPF 6 LiPF 6
  • L 1 BF 4 CH 3 COOH
  • the mixture preferably comprises at least one lithium salt A having the formula (I) R 1 -SO 2 -NK-SO 2 -R 2 in which R 1 and R 2 represent, independently of one of the other, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 11 , C 6 F 13 , C 7 F 15 , CeF 7 , or C 9 F 19 , with R and R 2 is preferably, independently of each other, F or CF 3, and more preferably F; and at least one potassium salt B selected from the group consisting of KPF 6 , KBF 4 , CH 3 COOK, CH 3 SO 3 K, CF 3 SO 3 K, CF 3 COOK, K 2 B 12 F 12 , K
  • the mixture preferably comprises at least one lithium salt A having the formula (I) R 1 -SO 2 -NK-SO 2 -R 2 in which R 1 and R 2 represent, independently of one of the other, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 11 , C 6 F 13 , C 7 F 15 , CeF 7 , or C 9 F 19 , with R and R 2 is preferably, independently of each other, F or CF 3, and more preferably F; and at least one potassium salt B having the formula (III) R 3 -SO 2 -NK-SO 2 -R 4 in which R 3 and R 4 represent, independently of one another, F, CF 3 , CHF 2 , CH 2
  • the mixture preferably comprises at least one lithium salt A having the formula (I) R 1 -SO 2 -NK-SO 2 -R 2 in which R 1 and R 2 represent, independently of one of the other, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 11 , C 6 F 13 , C 7 F 15 , CeF 7 , or C 9 F 19 , with R and R 2 is preferably, independently of each other, F or CF 3, and more preferably F; and at least one potassium salt B having the above-mentioned formula (IV) wherein Rp is F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2
  • the mixture preferably comprises at least one lithium salt A having the above-mentioned formula (II) in which Rf represents F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4, C 2 H 2 F 3 , C 2 H 3 F 2, C 2 F 5, C 3 F 7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CsF, or C 9 F 19, preferably Rf represents CF 3; and at least one potassium salt B selected from the group consisting of KPF 6 , KBF 4 , CH 3 COOK, CH 3 SO 3 K, CF 3 SO 3 K, CF 3 COOK, K 2 B 12 F 12 , KBC 4 O 8, and mixtures thereof, the potassium salt B being preferably KPF 6 .
  • Rf represents F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4, C 2 H 2 F 3 , C 2 H 3 F 2, C
  • the mixture preferably comprises at least one lithium salt A having the above-mentioned formula (II) in which Rf represents F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4, C 2 H 2 F 3 , C 2 H 3 F 2, C 2 F 5, C 3 F 7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F-I3, C7F15, CsF, or C 9 F 19, preferably Rf represents CF 3; and at least one potassium salt B having the formula (III) R 3 -SO 2 -NK-SO 2 -R 4 in which R 3 and R 4 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9
  • the mixture preferably comprises at least one lithium salt A having the above-mentioned formula (II) in which Rf represents F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4, C 2 H 2 F 3 , C 2 H 3 F 2, C 2 F 5, C 3 F 7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F-I3, C7F15, CsF, or C 9 F 19, preferably Rf represents CF 3; and at least one potassium salt B having the above-mentioned formula (IV) wherein Rp is F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3, C 2 H 3 F 2 , C 2 F 5, C 3 F 7, C 3 H 2 F 5, C 3 H 4 F 3, C 4 F 9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, Ce
  • the mixture of the invention is chosen from one of the following mixtures:
  • the mixture according to the invention can be prepared by mixing the various constituents either simultaneously or consecutively.
  • 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 at a temperature greater than or equal to 25 ° C., preferably of between 25 ° C. C and 80 ° C, and / or in particular at a tension of between 4 and 5, preferably at 4.2, 4.35, 4.4, 4.5 or 4.7 volts.
  • a battery for example a Li-ion battery
  • 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 invention also relates to an electrolyte composition, in particular for a battery such as for example 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 or other potassium salt than those mentioned above for the mixture.
  • the potassium and lithium salts mentioned above for the mixture 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 7 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 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
  • methyl ethers of oligoethylene glycols of 2 to 5 oxyethylene units dioxolane, dioxane, dibutyl ether, tetrahydrofuran, and their mixtures.
  • 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.
  • alcohols mention may be made, for example, of ethyl alcohol or isopropyl alcohol.
  • 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 electrolyte composition comprises one of the following mixtures: ethylene carbonate (EC) / propylene carbonate (PC) / dimethyl carbonate (DMC) in a 1/1/1 mass ratio;
  • EC ethylene carbonate
  • EMC methyl ethyl carbonate
  • 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 (C 2 O 4 ) 2 , lithium nitrate, alkyldisulfide, fluorotoluene, 1,4-dimethoxytetrafluorotoluene, t-butylphenol 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 cin
  • 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 electrolyte 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 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 battery, for example a Li-ion battery, in particular at a temperature greater than or equal to 25 ° C., preferably between 25 ° C and 80 ° C, and / or in particular at a voltage of between 4 and 5, preferably at 4.2, 4.35, 4.4, 4.5 or 4.7 volts.
  • a battery for example a Li-ion battery
  • a temperature greater than or equal to 25 ° C. preferably between 25 ° C and 80 ° C
  • a voltage of between 4 and 5 preferably at 4.2, 4.35, 4.4, 4.5 or 4.7 volts.
  • the use is made in mobile devices, for example the mobile phones, cameras, tablets or laptops, in electric vehicles, or in renewable energy storage.
  • 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.
  • the battery comprises several electrochemical cells according to the invention, said cells can be assembled in series and / or in parallel.
  • 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.
  • electronically conductive material means a material capable of driving the electrons.
  • the negative electrode of the electrochemical cell comprises, as an electrochemically active material, graphite, lithium, a lithium alloy, a lithium titanate of LUTisO ⁇ 1 or TiO 2 type , 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 positive electrode of the electrochemical cell comprises an electrochemically active material selected from manganese dioxide (MnC> 2 ), iron oxide, copper oxide, nickel oxide, lithium-manganese composite oxides (for example Li x Mn 2 O 4 or Li x MnC 2), lithium-nickel compositions (for example Li x NiC 2) oxides, lithium cobalt compositions (for example Li x CoC 2) ), composite oxides of lithium-nickel-cobalt (e.g.
  • LiNii- there CoyC> 2 lithium nickel composite oxides cobalt manganese
  • LFP LiFePCU
  • NMC LiMn x Co y Ni Z C> 2
  • NMC LiFePCUF
  • LiFeSCUF LiNi xi Co yi Al zi C> 2
  • 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 bin
  • Non-limiting examples of binders include linear, branched and / or crosslinked polymeric polyether binders (e.g., polymers based on polyethylene oxide (PEO), or poly (propylene oxide) (PPO) or a mixture of both (or an EO / PO co-polymer), 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
  • Some binders, such as those soluble in water, may also include an additive such as CMC (carboxymethylcellulose).
  • the salt mixture according to the invention advantageously makes it possible to improve the service life of the battery.
  • the present invention also relates to the use of at least one potassium salt B as defined above, in a mixture comprising at least 99% by weight of at least one lithium salt A as defined above ( preferably from 99% to 99.9999% by weight of at least one lithium salt A), to improve the life of a battery, in particular a Li-ion battery.
  • 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%.
  • the following table shows the oxidation currents at different voltages after two round trips in voltage for different amounts of potassium salt added. The two prior scans allow the formation of passivation layers such as SEI and passivation of aluminum.
  • the oxidation current observed can reflect many phenomena: aluminum corrosion, degradation of the electrolyte and the formation of lithium dendrites. All these phenomena are responsible for the degradation of the life of Li-ion batteries. The lower the current, the longer the life of the battery is improved.
  • the results show that the addition of KPF 6 to LiPF 6 advantageously makes it possible to reduce this oxidation current with respect to LiPF 6 alone, and thus to improve the service life of the batteries. Li-ion.
  • CR2032 button cells were manufactured equipped with a NMC1 11 cathode, a 8 mm diameter metal lithium pellet as anode and a 18 mm diameter fiberglass separator soaked with 12 drops (0.6 mL).
  • a 1 mol LiFSI lithium salt solution / additive with a KFSI potassium salt in a solvent mixture composed of ethylene carbonate and methyl ethyl carbonate (CAS 623-53-0) in a ratio 3/7 by volume.
  • This battery then undergoes two training cycles at a C / 20 rate to form the different passivation layers.
  • the battery is charged at C / 5 and discharged C / 2 at 25 ° C until the capacity reaches 80% of the initial capacity determined after the two training cycles.
  • the following table shows the number of cycles reached at 80% capacity for different grades of KFSI (mixed with LiFSI):

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EP19709545.8A 2018-01-29 2019-01-29 Mischung aus kalium- und lithiumsalzen und verwendung davon in einer batterie Pending EP3747076A2 (de)

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FR1850664A FR3077415B1 (fr) 2018-01-29 2018-01-29 Melange de sels de lithium et de potassium, et son utilisation dans une batterie
PCT/FR2019/050196 WO2019145662A2 (fr) 2018-01-29 2019-01-29 Melange de sels de lithium et de potassium, et son utilisation dans une batterie

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FR3059835B1 (fr) * 2016-12-02 2020-01-24 Arkema France Amelioration de la conductivite ionique d'electrolyte a base de sels de lithium d'imidazolate
CN112201855B (zh) * 2020-10-19 2022-04-01 宁德新能源科技有限公司 电解液、电化学装置和电子装置
CN112448037A (zh) * 2020-11-30 2021-03-05 广州天赐高新材料股份有限公司 一种补锂组合物、补锂电解液、锂二次电池补锂方法
CN115196646A (zh) * 2022-08-23 2022-10-18 江苏瀚康电子材料有限公司 一种四氟硼酸锂的合成方法

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US5691083A (en) * 1995-06-07 1997-11-25 Eveready Battery Company, Inc. Potassium ion additives for voltage control and performance improvement in nonaqueous cells
JP3309719B2 (ja) * 1996-07-10 2002-07-29 松下電器産業株式会社 非水電解液二次電池
CA2199446A1 (fr) * 1997-03-07 1998-09-07 Yves Choquette Generateurs a electrolyte polymere possedant un sel de potassium permettant de stabiliser les performances et la vie utile de la batterie
USRE37805E1 (en) * 1997-03-12 2002-07-23 Hydro-Quebec Polymer electrolyte lithium battery containing a potassium salt
CN101300651B (zh) 2005-11-04 2012-07-04 斯泰拉化工公司 蓄电元件
CN101548425A (zh) * 2006-12-06 2009-09-30 三菱化学株式会社 非水系电解液和非水系电解液二次电池
CN101241774B (zh) * 2007-02-09 2010-11-10 中国科学院物理研究所 一种复合电解质组合物及其制备方法
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JP2014024786A (ja) 2012-07-26 2014-02-06 Mitsubishi Materials Corp パーフルオロアルキルスルホン酸金属塩の製造方法及びパーフルオロアルキルスルホン酸金属塩、これを利用したリチウムイオン電池用の電解質並びに樹脂用の導電性付与剤
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WO2015132892A1 (ja) 2014-03-05 2015-09-11 株式会社日立製作所 リチウムイオン二次電池用電解質液およびそれを用いたリチウムイオン二次電池

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US20200212488A1 (en) 2020-07-02
KR102289777B1 (ko) 2021-08-12
WO2019145662A2 (fr) 2019-08-01
PL434847A1 (pl) 2021-05-17
KR20200116897A (ko) 2020-10-13
HUP2000261A1 (hu) 2020-12-28
JP7355744B2 (ja) 2023-10-03
JP2021511640A (ja) 2021-05-06
CN111316493A (zh) 2020-06-19
FR3077415B1 (fr) 2020-07-24
CN111316493B (zh) 2021-07-13
FR3077415A1 (fr) 2019-08-02

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