• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a blend comprising: from 99% to 99.9999% by weight of at least one lithium salt A; and from 1 ppm to 10,000 ppm by weight of at least one potassium salt B. The present invention also relates to the use of said mixture in a battery.
    公开号:FR3077415A1
    申请号:FR1850664
    申请日:2018-01-29
    公开日:2019-08-02
    发明作者:Gregory Schmidt
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    MIXTURE OF LITHIUM AND POTASSIUM SALTS AND ITS USE IN A BATTERY
    FIELD OF THE INVENTION
    The present application relates to a mixture of lithium and potassium salts, as well as its use in a battery.
    TECHNICAL BACKGROUND
    Typically, a battery (such as for example a lithium-ion battery or a Li-Suffer 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.
    In the field of batteries, the passivation layers formed during the first charge-discharge cycles are essential for the life of the battery. As passivation layers, mention may in particular be made of the passivation layer on aluminum which is the current collector used at the cathode, or also the "Solid Electrolyte Interface" (SEI) which is the inorganic and polymeric layer which forms at the anode / electrolyte and cathode / electrolyte interface. If the passivation layers are poorly formed and / or are not stable, their reformation during charge / discharge cycles is responsible for the reduction of the battery life: indeed, part of the current will be used to reform these passivation layers rather than participate in battery life. The formation of dendrites on a lithium metal anode also causes a decrease in the life of the battery.
    There is therefore a need to remedy the aforementioned drawbacks, and in particular to improve the lifespan of batteries, in particular Li-ion type batteries.
    DESCRIPTION OF THE INVENTION
    Mixed
    The present application relates to a mixture comprising (preferably consisting essentially of, and preferably consisting of):
    • i) from 99% to 99.9999% by weight of at least one lithium salt A chosen from the group consisting of LiPF6; L1BF4; CH3COOL1; CH3SO3L1; CF3SO3L1;
    CF3COOU; L12B12F12; UBC4O8; a salt of the following formula (I): R1-SO2-NUSO2-R2 (I) in which Ri and R 2 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, CeFi3, C7F15, C 8 Fi7, or C9F19; a salt of the following formula (II):
    (H) in which Rf represents F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or9 and their mixtures;
    Ii) from 1 ppm to 10,000 ppm by weight of at least one potassium salt B chosen from the group consisting of KPF6; KBF4; CH 3 COOK; CH3SO3K; CF3SO3K; CF3COOK; K2B12F12; KBC4O8; of a salt of the following formula (III): R3-SO2-NKSO2-R4 (III) in which R3 and R4 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19; a salt of the following formula (IV):
    (IV) in which Rp represents F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5,
    C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19; and their mixtures.
    In the context of the invention, the term "ppm" or "part per million" means ppm by weight.
    According to one embodiment, the mixture comprises:
    i) from 99.1% to 99.9999% by weight, preferably from 99.2% to 99.9999% by weight, preferably from 99.3% to 99.9999% by weight, advantageously from 99.4% by weight at 99.9999% by weight, even more preferably from 99.5% to 99.9999% by weight, even more advantageously from 99.6% by weight to 99.9999% by weight, preferably from 99, 7% to 99.9999% by weight, for example from 99.8% to 99.9999% by weight, and in particular from 99.9% to 99.9999% by weight of at least one of the lithium salts mentioned above , and / or ii) from 1 ppm to 9,000 ppm, preferably from 1 to 8,000 ppm, preferably from 1 to 7,000 ppm, advantageously from 1 to 6,000 ppm, even more preferably from 1 to 5,000 ppm, again more advantageously from 1 to 4,000 ppm, preferably from 1 to 3,000 ppm, for example from 1 to 2,000 ppm, and in particular from 1 to 1,000 ppm of at least one potassium salt B mentioned above.
    According to one embodiment, 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%, preferably greater than or equal to 99.9%, advantageously greater than or equal to 99.95%, even more preferably greater than or equal to 99.99%, even more advantageously greater than or equal to 99.995%, in a preferred manner greater or equal to 99.999%, for example greater than or equal to 99.9995% by weight relative to the total weight of the mixture.
    According to one embodiment, the mixture comprises at least one potassium salt B as defined above, in a mass content 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, preferably 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.
    According to one embodiment, the mixture comprises:
    i) from 99% to 99.999% by weight, preferably from 99.5% to 99.999% by weight, preferably from 99.7% to 99.999% by weight, advantageously from 99.85% by weight to 99.999% by weight, even more preferably from 99.85% to 99.995% by weight, even more advantageously from 99.9% by weight to 99.99% by weight of at least one lithium salt A mentioned above, and / or ii) of 10 ppm at 10,000 ppm, preferably from 10 to 5,000 ppm, preferably from 10 to 3,000 ppm, advantageously from 10 to 1,500 ppm, even more preferably from 50 to 1,500 ppm, even more advantageously from 100 to 1,000 ppm d '' at least one potassium salt B mentioned above.
    According to one embodiment, the mixture comprises at least one lithium salt A and at least one potassium salt B, said salts having the same anion. For example, the mixture can comprise LiPF6 and KPF6 (the common anion being PF6 - ), or the mixture can comprise a salt of formula (I) in which Ri = R 2 = F, and a salt of formula (III ) in which R3 = R4 = F.
    According to one embodiment, the mixture preferably comprises at least lithium salt A chosen from the group consisting of LiPF6, L1BF4, CH3COOU, CHsSChLi, CF3SO3L1, CF3COOU, L12B12F12, L1BC4O8, and their mixtures, the lithium salt A being preferably LiPF6; and at least one potassium salt B chosen from the group consisting of KPF6, KBF4, CH3COOK, CH3SO3K, CF3SO3K, CF3COOK, K2B12F12, KBC4O8, and their mixtures, the potassium salt B preferably being KPF6.
    According to one embodiment, the mixture preferably comprises at least lithium salt A chosen from the group consisting of LiPF6, L1BF4, CH3COOU, CHsSChLi, CF3SO3L1, CF3COOU, L12B12F12, L1BC4O8, and their mixtures, the lithium salt A being preferably LiPF6; and at least one potassium salt B having the formula (III) R3-SO2-NK-SO2-R4 in which R3 and R4 represent, independently of one another, F, CF3, CHF2, CH2F, C2HF4, C2H2F3 , C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19. With R3 and R4 preferably representing, independently of one another, F or CF3, and preferably F.
    According to one embodiment, the mixture preferably comprises at least lithium salt A chosen from the group consisting of LiPF6, L1BF4, CH3COOU, CH3SO3L1, CF3SO3L1, CF3COOU, L12B12F12, L1BC4O8, and their mixtures, the lithium salt A being preferably LiPF6; and at least one potassium salt B having the above formula (IV) in which Rp represents F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, CeFn , C7F15, C 8 Fi7, or C9F19, Rp preferably representing CF 3 .
    According to one embodiment, the mixture preferably comprises at least lithium salt A having the formula (I) R1-SO2-NK-SO2-R2 in which Ri and R 2 represent, independently of one another, F , CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, CeFn, C7F15, CeFi7, or C9F19, preferably with Ri and R 2 representing , independently of one another, F or CF3, and preferably F; and at least one potassium salt B chosen from the group consisting of KPF6, KBF4, CH3COOK, CH3SO3K, CF3SO3K, CF3COOK, K2B12F12, KBC4O8, and mixtures thereof, the potassium salt preferably being KPF6.
    According to one embodiment, the mixture preferably comprises at least lithium salt A having the formula (I) R1-SO2-NK-SO2-R2 in which Ri 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 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C5F11, C 3 Fi 3 , C 7 Fis, CsFi 7 , or C9F19, with Ri and R 2 preferably representing, independently from each other, F or CF 3 , and 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 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 , C5F11, C 3 Fi 3 , C 7 Fis, CsFi 7 , or C9F19, with R 3 and R 4 preferably representing, independently one on the other, F or CF 3 , and preferably F.
    According to one embodiment, the mixture preferably comprises at least lithium salt A having the formula (I) Ri-SO 2 -NK-SO 2 -R 2 in which Ri and R 2 independently represent 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 , C5F11, C 3 Fi 3 , C 7 Fis, CsFi 7 , or C9F19, with Ri and R 2 representing preferably, independently of one another, F or CF 3 , and preferably F; and at least one potassium salt B having the above formula (IV) in which Rp 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 Fs, C 3 F 7 , C 3 H 2 Fs, C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C5F11, CeFi 3 , C 7 Fi 5 , C 3 Fi 7 , or C9F19, Rp preferably representing CF 3 .
    According to one embodiment, the mixture preferably comprises at least lithium salt A having the above 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 , C 3 H 2 F5, C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F5, C5F11, C 3 Fi 3 , C 7 Fis, C 3 Fi 7 , or C9F19, Rf preferably representing CF 3 ; and at least one potassium salt B chosen from the group consisting of KPF6, KBF 4 , CH 3 COOK, CH 3 SO 3 K, CF 3 SO 3 K, CF 3 COOK, K 2 Bi 2 Fi 2 , KBC 4 Os, and mixtures thereof, the potassium salt B preferably being KPF6.
    According to one embodiment, the mixture preferably comprises at least lithium salt A having the above 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 , C 3 H 2 F5, C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F5, C5F11, CeFi 3 , C 7 Fis, C 3 Fi 7 , or C9F19, Rf preferably representing 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 , C 4 H 2 F 7 , C 4 H 4 F 5 , C5F11, CeFi 3 , C 7 Fi 5 , C 3 Fi 7 , or CgFw. With R 3 and R 4 preferably representing, independently of the one of the other, F or CF 3 , and preferably F.
    According to one embodiment, the mixture preferably comprises at least lithium salt A having the above 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 , C 3 H 2 F5, C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F5, C5F11, CeFi 3 , C 7 Fis, C 3 Fi 7 , or C9F19, Rf preferably representing CF 3 ; and at least one potassium salt B having the above formula (IV) in which Rp represents F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 ,
    C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19, Rp preferably representing CF3.
    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 between 25 °. C and 80 ° C, and / or in particular at a voltage between 4 and 5, preferably at 4.2, 4.35, 4.4, 4.5 or 4.7 volts. For example, it is used in portable devices, such as cell phones, cameras, tablets or laptops, in electric vehicles, or in the storage of renewable energy.
    Electrolyte composition
    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.
    Preferably, the electrolyte composition does not comprise any other alkali or alkanine earth salt than those of the above-mentioned mixture.
    Preferably, the electrolyte composition does not comprise any other lithium salt or any other potassium salt than those mentioned above for the mixture.
    Preferably, the potassium and lithium salts mentioned above for the mixture represent 100% of the totality of the salts present in the composition.
    In the context of the invention, interchangeably used "electrolyte composition", "electrolyte" and "electrolytic composition".
    According to a preferred embodiment, the electrolyte composition comprises from 1% to 99% by mass of the above-mentioned mixture, preferably from 5% to 99%, and advantageously from 20% to 95%, relative to the total mass of the composition.
    According to a preferred embodiment, the electrolyte composition comprises from 1% to 99% by mass of solvent, preferably from 5% to 99%, and advantageously from 20% to 95%, relative to the total mass of the composition.
    According to one embodiment, the molar concentration of the above-mentioned 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, preferably 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.
    According to one embodiment, the electrolyte composition can comprise a solvent or a mixture of solvents, such as for example two, three or four different solvents.
    The solvent for the electrolyte composition may be a liquid solvent, optionally gelled by a polymer, or a polar polymer solvent optionally plasticized by a liquid.
    According to one embodiment, the solvent is an organic solvent, preferably aprotic. Preferably, the solvent is a polar organic solvent.
    According to one embodiment, the solvent is chosen from the group consisting of ethers, carbonates, esters, ketones, partially hydrogenated hydrocarbons, nitriles, amides, alcohols, sulfoxides, sulfolane, nitromethane, 1,3dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1, H) -pyrimidinone, 3methyl-2-oxazolidinone, and mixtures thereof.
    Among the ethers, mention may be made of linear or cyclic 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.
    Among the esters, mention may be made of phosphoric acid esters or sulfite esters. Mention may for example be made of methyl formate, methyl acetate, methyl propionate, ethyl acetate, butyl acetate, gamma butyrolactone or their mixtures.
    Among the ketones, mention may in particular be made of cyclohexanone.
    Among the alcohols, mention may, for example, be made of ethyl alcohol and isopropyl alcohol.
    Among the nitriles, mention may be made, for example, of acetonitrile, pyruvonitrile, propionitrile, methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methonitrileitrile , 3-methylglutaronitrile, adiponitrile, malononitrile, and mixtures thereof.
    Among the carbonates, mention may be made, for example, of 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 ethyl carbonate (EMC) (CAS: 623-53-0), diphenyl carbonate (CAS 102-09-0), methyl phenyl carbonate (CAS: 13509-27-8), carbonate dipropyl (DPC) (CAS: 623-96-1), methyl propyl carbonate (MPC) (CAS: 1333-41-1), ethyl propyl carbonate (EPC), carbonate vinylene (VC) (CAS: 872-36-6), fluoroethylene carbonate (FEC) (CAS: 114435-02-8), trifluoropropylene carbonate (CAS: 167951-80-6) or their mixtures.
    The particularly preferred solvent is chosen from carbonates and their mixtures.
    According to one embodiment, 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;
    ethylene carbonate (EC) / propylene carbonate (PC) / diethyl carbonate (DEC) in a 1/1/1 mass ratio;
    ethylene carbonate (EC) / propylene carbonate (PC) / methyl ethyl carbonate (EMC) in a 1/1/1 mass ratio;
    ethylene carbonate (EC) / dimethyl carbonate (DMC) in a 1/1 mass ratio;
    ethylene carbonate (EC) / diethyl carbonate (DEC) in a 1/1 mass ratio;
    ethylene carbonate (EC) / methyl ethyl carbonate (EMC) in a 1/1 mass ratio;
    ethylene carbonate (EC) / dimethyl carbonate (DMC) in a mass ratio in a volume ratio 3/7;
    ethylene carbonate (EC) / diethyl carbonate (DEC) in a 3/7 volume ratio;
    ethylene carbonate (EC) / methyl ethyl carbonate (EMC) in a volume ratio 3/7;
    Dioxolane (DOL) / dimethoxyethane (DME) in a 2/1 volume ratio; Dioxolane (DOL) / dimethoxyethane (DME) in a volume ratio 1/1.
    According to one embodiment, the electrolyte composition comprises at least one electrolytic additive.
    Preferably, the electrolytic additive is chosen 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 (C2O4) 2, lithium nitrate, alkyldisulfide, fluorotoluene, 1,4dimethoxytetrafluorotoluene, t-butylphenol, di-t-butylphenol, tris (pentafluorophenyl) borane, oximes, aliphatic epoxides, halogenated biphenyls, metacrylic acids, allyl ethyl carbonate, vinyl acetate, divinyl adipate, acrylonitrile, 2 -vinylpyridine, maleic anhydride, methyl cinnamate, phosphonates, vinyl-containing silane compounds, 2cyanofuran and their mixtures, the electrolytic additive preferably being fluoroethylene carbonate (FEC).
    For example, the content of electrolyte additive in the electrolyte composition is between 0.01% and 10%, preferably between 0.1% and 4% by mass relative to the total mass of the electrolyte composition. In particular, the content of electrolyte additive in the electrolyte composition is less than or equal to 2% by mass 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 can be prepared by any means known to those skilled in the art, for example by dissolving, preferably with stirring, the 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 between 4 and 5, preferably at 4.2, 4.35, 4.4, 4.5 or 4.7 volts. For example, it is used in portable devices, such as cell phones, cameras, tablets or laptops, in electric vehicles, or in the storage of renewable energy.
    Electrochemical cell
    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 can 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.
    In the context of the invention, by negative electrode is meant the electrode which acts as an anode, when the battery delivers current (that is to say when it is in the process of discharging) and which makes cathode office when the battery is in the process of charging.
    The negative electrode typically includes an electrochemically active material, optionally an electronic conductive material, and optionally a binder.
    In the context of the invention, the term "electrochemically active material" means a material capable of reversibly inserting ions.
    In the context of the invention, the term "electronic conductive material" means a material capable of conducting electrons.
    According to one embodiment, the negative electrode of the electrochemical cell comprises, as the electrochemically active material, graphite, lithium, a lithium alloy, a lithium titanate of the LÎ4TÎ50i2 or T1O2 type, silicon or a lithium alloy and silicon, a tin oxide, an intermetallic lithium compound, or a mixture thereof.
    The negative electrode can comprise lithium, which can then consist of a metallic lithium film or of an alloy comprising lithium. An example of a negative electrode may include a bright lithium film prepared by rolling, between rollers, a lithium strip.
    In the context of the invention, by positive electrode is meant the electrode which acts as a cathode, when the battery delivers current (that is to say when it is in the process of discharging) and which acts as anode when the battery is charging.
    The positive electrode typically includes an electrochemically active material, optionally an electronic conductive material, and optionally a binder.
    In another embodiment, the positive electrode of the electrochemical cell comprises an electrochemically active material chosen from manganese dioxide (MnCk), iron oxide, copper oxide, nickel oxide, oxides lithiummanganese composites (for example LixM ^ CU or LixMnCk), lithium-nickel composition oxides (for example Li x NiO2), lithium-cobalt composition oxides (for example LixCoCk), lithium-nickel-cobalt composite oxides (for example LiNii .yCoyCk), lithium-cobalt-manganese composite oxides (for example LiNi x Mn y Co z O2 with x + y + z = 1), lithium-nickel-cobalt-manganese composite oxides enriched in lithium (for example Lii + x (NixMn y Co z ) i.xO2), composite oxides of lithium and transition metal, composite oxides of lithium-manganese-nickel with spinel structure (for example LixMn ^ yNiyCU), oxides of lithium-phosphorus olivine structure (for example LixFePCU, Li x Fei.yMn y PO4 or LixCoPCU ), iron sulphate, vanadium oxides, and mixtures thereof.
    Preferably, the positive electrode comprises an electrochemically active material chosen from LiCoCk, LiFePCU (LFP), LiMn x Co y Ni z O2 (NMC, with x + y + z = 1), LiFePCUF, LiFeSCUF, LiNi x iCo y iAl z iO2 (NCA, withxi + yi + zi = 1) and their mixtures.
    The positive electrode material may also include, in addition to the electrochemically active material, an electronic conductive material such as a carbon source, including, for example, carbon black, Ketjen® carbon, Shawinigan carbon, graphite, graphene, carbon nanotubes, carbon fibers (such as carbon fibers formed in the gas phase (VGCF), non-powdery carbon obtained by carbonization of an organic precursor, or a combination of two or more of these. D Other additives may also be present in the material of the positive electrode, such as lithium salts or inorganic particles of the ceramic or glass type, or even other compatible active materials (for example, sulfur).
    The material of the positive electrode may also include a binder. Nonlimiting examples of binders include linear, branched and / or crosslinked polyether polymeric binders (e.g., polymers based on poly (ethylene oxide) (PEO), or poly (propylene oxide) (PPO) or d a mixture of the two (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. binders, such as those soluble in water, can also include an additive like CMC (carboxymethylcellulose).
    The mixture of salts according to the invention advantageously makes it possible to improve the 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.
    In the context of the invention, by "between x and y" or "between x and y", we mean an interval in which the limits x and y are included. For example, the range "between 1% and 98%" or "ranging from 1% to 98%" includes in particular the values 1 and 98%.
    All of the embodiments described above can be combined with each other.
    The following examples illustrate the invention without, however, limiting it.
    EXPERIMENTAL PART
    Cyclic voltammetry tests were carried out. For this, CR2032 button cells were manufactured fitted with an aluminum foil with a diameter of 20 mm as working electrode, with a lithium metal pellet with a diameter of 8 mm as reference electrode and with a fiberglass separator of diameter 18 mm soaked with 12 drops (0.6 mL) of a LiPF6 lithium salt solution at 1 mol / L added with a potassium salt KPFIn a mixture of solvent composed of ethylene carbonate and ethyl carbonate methyl (CAS = 62353-0) in a 3/7 by volume ratio. Then a voltage sweep is carried out at the terminals of the button cell and the current generated is measured and recorded. The voltage sweep is carried out at 4 V and at 4.2 V. The following table shows the oxidation currents at different voltages after two roundtrip sweeps in voltage for different quantities of potassium salt added. The two preliminary scans allow the formation of passivation layers such as SEI and passivation of aluminum.
    voltage (V) 4 4.2 LiPF6 alone 28.5 pA 23.4 pA LiPFe + 10,000 ppm KPF 6 5.7 pA 6.15 pA LiPFe + 1000 ppm KPF 6 7.5 pA 8.3 pA LiPFe + 100 ppm KPF6 11 pA 12 pA LiPFe +10 ppm KPF6 17.8 pA 16.4 pA
    The oxidation current observed can reflect many phenomena: corrosion of aluminum, degradation of the electrolyte and the formation of lithium dendrites. All these phenomena are responsible for the degradation of the lifespan of Li-ion batteries. The lower the current, the longer the life of the battery. At 4 V and 4.2 V, the results show that the addition of KPF6 to LiPF6 advantageously makes it possible to reduce this oxidation current compared to LiPF6 alone, and therefore to improve the lifespan of Li-ion batteries. .
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Mixture comprising:
    • from 99% to 99.9999% by weight of at least one lithium salt A chosen from the group consisting of LiPF6; L1BF4; CH3COOL1; CH3SO3L1; CF3SO3L1; CF3COOU; L12B12F12; UBC4O8; a salt of the following formula (I): R1-SO2-NUSO2-R2 (I) in which Ri and R2 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C2HF4 , C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, CeFi3, C7F15, C 8 Fi7, or C9F19; a salt of the following formula (II):
    in which Rf represents F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5,
    C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19; and their mixtures;
    • from 1 ppm to 10,000 ppm by weight of at least one potassium salt B chosen from the group consisting of KPF6; KBF4; CH 3 COOK; CH3SO3K; CF3SO3K; CF3COOK; K2B12F12; KBC4O8; a salt of the following formula (III): R3-SO2-NKSO2-R4 (III) in which R3 and R4 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5,
    C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19; a salt of the following formula (IV):
    in which Rp represents F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5,
    C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19; and their mixtures.
    [2" id="c-fr-0002]
    2. Mixture according to claim 1, comprising:
    from 99.1% to 99.9999% by weight, preferably from 99.2% to 99.9999% by weight, preferably from 99.3% to 99.9999% by weight, advantageously from 99.4% by weight to 99.9999% by weight, even more preferably from 99.5% to 99.9999% by weight, even more advantageously from 99.6% by weight to 99.9999% by weight, preferably from 99.7% to 99.9999% by weight, for example from 99.8% to 99.9999% by weight, and in particular from 99.9% to 99.9999% by weight of at least one lithium salt A, and / or from 1 ppm to 9000 ppm, preferably from 1 to 8000 ppm, preferably from 1 to 7000 ppm, advantageously from 1 to 6000 ppm, even more preferably from 1 to 5000 ppm, even more advantageously from 1 to 4,000 ppm, preferably from 1 to 3,000 ppm, for example from 1 to 2,000 ppm, and in particular from 1 to 1,000 ppm of at least one potassium B salt.
    [3" id="c-fr-0003]
    3. Mixture according to any one of claims 1 or 2, comprising:
    From 99% to 99.999% by weight, preferably from 99.5% to 99.999% by weight, preferably from 99.7% to 99.999% by weight, advantageously from 99.85% by weight to 99.999% by weight, again more preferably from 99.85% to 99.995% by weight, even more advantageously from 99.9% by weight to 99.99% by weight of at least one lithium salt A, and / or • from 10 ppm to 10,000 ppm, preferably from 10 to 5000 ppm, preferably from 10 to 3000 ppm, advantageously from 10 to 1500 ppm, even more preferably from 50 to 1500 ppm, even more advantageously from 100 to 1000 ppm at least potassium salt B.
    [4" id="c-fr-0004]
    4. Mixture according to any one of claims 1 to 3, in which the lithium salt A and the potassium salt B have the same anion.
    [5" id="c-fr-0005]
    5. Mixture according to any one of claims 1 to 4, in which:
    • the lithium salt A is chosen from the group consisting of LiPF6, L1BF4, CH3COOU, CHsSChLi, CF3SO3L1, CF3COOL1, L12B12F12, UBC4O8, and their mixtures, the lithium A salt preferably being LiPF6; and the potassium salt B is chosen from the group consisting of KPF 6 , KBF 4 , CH3COOK, CH3SO3K, CF3SO3K, CF3COOK, K2B12F12, KBC4O8, and mixtures thereof, the potassium salt B preferably being KPF 6 ;
    or • the lithium salt A is chosen from the group consisting of LiPF6, L1BF4, CH3COOU, CHsSChLi, CF3SO3L1, CF3COOL1, L12B12F12, UBC4O8, and mixtures thereof, the lithium salt preferably being LiPF6; and the potassium salt B has the formula (III) R3-SO2-NK-SO2-R4 in which R3 and R4 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19, preferably with R3 and R4 independently of one another, F or CF3, and preferably F;
    or • the lithium salt A is chosen from the group consisting of LiPF6, L1BF4, CH3COOU, CH3SO3L1, CF3SO3L1, CF3COOL1, L12B12F12, UBC4O8, and their mixtures, the lithium salt preferably being LiPF6; and the potassium salt B has the formula (IV) as defined in claim 1, in which Rp represents F, CF3, CHF2, CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, CeFi3, C7F15, C 8 Fi7, or C9F19, Rp preferably representing CF 3 ;
    or • the lithium salt A has the formula (I) R1-SO2-NK-SO2-R2 in which Ri and R2 represent, independently of one another, F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, C 8 Fi7, or C9F19, with Ri and R2 preferably representing, independently of one another, F or CF3, and preferably F; and the potassium salt B is chosen from the group consisting of KPF6, KBF4, CH3COOK, CH3SO3K, CF3SO3K, CF3COOK, K2B12F12, KBC4O8, and mixtures thereof, the potassium salt preferably being KPF6;
    or • the lithium salt A has the formula (I) R1-SO2-NK-SO2-R2 in which Ri and R2 represent, independently of one another, F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, C 8 Fi7, or C9F19, with Ri and R2 preferably representing, independently of one another, F or CF3, and preferably F; and the potassium salt B has the formula (III) R3-SO2-NK-SO2-R4 in which R3 and R4 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, CeFi7, or C9F19, preferably with R3 and R4 independently of one another, F or CF3, and preferably F;
    or • the lithium salt A has the formula (I) R1-SO2-NK-SO2-R2 in which Ri and R2 represent, independently of one another, F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C6F13, C7F15, C 8 Fi7, or C9F19, with Ri and R2 preferably representing, independently of one another, F or CF3, and preferably F; and the potassium salt B has the formula (IV) as defined in claim 1, in which Rp represents F, CF3, CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9 , C4H2F7, C4H4F5, C5F11, CeFi3, C7F15, C 8 Fi7, or C9F19, Rp preferably representing CF 3 ; or • the lithium salt A has the above formula (II) in which Rf represents F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C 6 Fi3, C7F15, C 8 Fi7, or C9F19, Rf preferably representing CF3; and the potassium salt B is chosen from the group consisting of KPF6, KBF4, CH3COOK, CH3SO3K, CF3SO3K, CF3COOK, K2B12F12, KBC 4 O 8 , and their mixtures, the potassium salt B preferably being KPF6;
    or • the lithium salt A has the formula (II) as defined in claim 1, in which Rf represents F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3 , C4F9, C4H2F7, C4H4F5, C5F11, C 6 Fi3, C7F15, C 8 Fi7, or C9F19, Rf preferably representing CF3; and the potassium salt B has the formula (III) R3-SO2NK-SO2-R4 in which R3 and R4 represent, independently of one another, F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3 , C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C 6 Fi3, C7F15, C 8 Fi7, or CgFw. With R 3 and R 4 preferably representing, independently of each other , F or CF3, and preferably F;
    or • the lithium salt A has the formula (II) as defined in claim 1, in which Rf represents F, CF 3 , CHF 2 , CH 2 F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3 , C4F9, C4H2F7, C4H4F5, C5F11, C 6 Fi3, C7F15, C 8 Fi7, or C9F19, Rf preferably representing CF3; and the potassium salt B has the formula (IV) as defined in claim 1, in which Rp represents F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C 6 Fi3, C7F15, C 8 Fi7, or C9F19, Rp preferably representing CF 3 .
    [6" id="c-fr-0006]
    6. An electrolyte composition, in particular for a battery such as for example a Li-ion battery, comprising the mixture as defined according to any one of claims 1 to 5, at least one solvent, and optionally at least one electrolytic additive.
    [7" id="c-fr-0007]
    7. Composition according to claim 6, comprising:
    from 1% to 99% by mass of the above-mentioned mixture, preferably from 5% to 99%, and advantageously from 20% to 95%, relative to the total mass of the composition; and / or from 1% to 99% by mass of solvent, preferably from 5% to 99%, and advantageously from 20% to 95%, relative to the total mass of the composition.
    [8" id="c-fr-0008]
    8. Composition according to any one of claims 6 or 7, in which the molar concentration of the mixture as defined in any one of claims 1 to 5 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, preferably less than or equal to 1.5 mol / L, and in particular less than or equal to 1.1 mol / L, for example less or equal to 1 mol / L.
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 6 to 8, in which the solvent is chosen from the group consisting of ethers, carbonates, esters, ketones, partially hydrogenated hydrocarbons, nitriles, amides, alcohols, sulfoxides, sulfolane, nitromethane, 1,3dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1, H) pyrimidinone, 3-methyl -2-oxazolidinone, and mixtures thereof.
    [10" id="c-fr-0010]
    10. Composition according to any one of claims 6 to 9, comprising one of the following solvent mixtures:
    ethylene carbonate (EC) / propylene carbonate (PC) / dimethyl carbonate (DMC) in a 1/1/1 mass ratio;
    ethylene carbonate (EC) / propylene carbonate (PC) / diethyl carbonate (DEC) in a 1/1/1 mass ratio;
    ethylene carbonate (EC) / propylene carbonate (PC) / methyl ethyl carbonate (EMC) in a 1/1/1 mass ratio;
    ethylene carbonate (EC) / dimethyl carbonate (DMC) in a 1/1 mass ratio;
    ethylene carbonate (EC) / diethyl carbonate (DEC) in a 1/1 mass ratio;
    ethylene carbonate (EC) / methyl ethyl carbonate (EMC) in a 1/1 mass ratio;
    ethylene carbonate (EC) / dimethyl carbonate (DMC) in a mass ratio in a volume ratio 3/7;
    ethylene carbonate (EC) / diethyl carbonate (DEC) in a 3/7 volume ratio;
    ethylene carbonate (EC) / methyl ethyl carbonate (EMC) in a volume ratio 3/7;
    Dioxolane (DOL) / dimethoxyethane (DME) in a 2/1 volume ratio; Dioxolane (DOL) / dimethoxyethane (DME) in a volume ratio 1/1.
    [11" id="c-fr-0011]
    11. Composition according to any one of claims 6 to 10, in which the electrolytic additive is chosen 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 (C2O4) 2, lithium nitrate, alkyldisulfide, fluorotoluene, 1,4 -dimethoxytetrafluorotoluene, t-butylphenol, di-tbutylphenol, tris (pentafluorophenyl) borane, oximes, aliphatic epoxides, halogenated biphenyls, metacrylic acids, allyl ethyl carbonate, vinyl acetate, divinyl adipate, acrylonitrile, 2-vinylpyridine, maleic anhydride, methyl cinnamate, phosphonates, vinyl-containing silane compounds, 2-cyanofuran and mixtures thereof, the electrolytic additive preferably being the flu carbonate oroethylene (FEC).
    [12" id="c-fr-0012]
    12. Use of a mixture according to any one of claims 1 to 5, or of an electrolyte composition according to any one of claims 6 to 11, 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 between 4 and 5, preferably at 4.2, 4.35, 4 , 4, 4.5 or 4.7 volts.
    [13" id="c-fr-0013]
    13. Electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte composition according to any one of claims 6 to 11, interposed between the negative electrode and the positive electrode, or a mixture as defined according to l 'any of claims 1 to 5.
    [14" id="c-fr-0014]
    14. Battery comprising at least one electrochemical cell according to claim
    13.
    [15" id="c-fr-0015]
    15. 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 in claim 1, to improve the duration of life of a battery, in particular a Li-ion battery.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3340361A1|2018-06-27|Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same
    EP2729978B1|2015-04-22|Lithium/sulphur accumulator
    EP3747076A2|2020-12-09|Mixture of potassium and lithium salts, and use thereof in a battery
    EP2721682B1|2015-09-09|Liquid electrolyte for a lithium battery, comprising a quaternary mixture of non-aqueous organic solvents
    EP3665737A1|2020-06-17|Lithium salt mixture and uses thereof as a battery electrolyte
    WO2018163127A1|2018-09-13|Electrolyte composition and use thereof in lithium-ion batteries
    FR3064822B1|2019-06-07|MIXTURE OF LITHIUM SALTS AND USES THEREOF AS BATTERY ELECTROLYTE
    CN1167165C|2004-09-15|Non-aqueous electrolyte secondary battery and mfg. method thereof
    WO2020234538A1|2020-11-26|Electrolyte composition containing a mixture of lithium salts
    EP3714498A1|2020-09-30|Use of a salt mixture as an additive in a lithium-gel battery
    FR3098214A1|2021-01-08|MIXTURE OF LITHIUM AND POTASSIUM SALTS, AND ITS USE IN A BATTERY
    EP3549192B1|2021-06-09|Improving the ion conductivity of an electrolyte based on lithium imidazolate salts
    EP2959530B1|2017-03-15|Electrochemical cell for a lithium-ion battery including a negative electrode made of silicon and a specific electrolyte
    EP2721683B1|2015-07-29|Liquid electrolyte for lithium accumulator, comprising a ternary mixture of non-aqueous organic solvents
    FR3063836A1|2018-09-14|ELECTROLYTE COMPOSITION AND ITS USE IN LITHIUM-ION BATTERIES
    CA2960489A1|2018-09-10|Electrolyte composition and its use in lithium-ion batteries
    FR3103637A1|2021-05-28|LITHIUM SALT ELECTROLYTE
    WO2021013559A1|2021-01-28|Electrolyte composition for an electrochemical component comprising a lithium anode
    CA3081892A1|2019-05-23|Use of lithium nitrate as the sole lithium salt in a lithium-gel battery
    FR3095551A1|2020-10-30|Electrolyte for an electrochemical accumulator comprising a particular ionic liquid
    同族专利:
    公开号 | 公开日
    PL434847A1|2021-05-17|
    US20200212488A1|2020-07-02|
    FR3077415B1|2020-07-24|
    CN111316493A|2020-06-19|
    JP2021511640A|2021-05-06|
    HU2000261A1|2020-12-28|
    CN111316493B|2021-07-13|
    EP3747076A2|2020-12-09|
    WO2019145662A3|2019-10-31|
    WO2019145662A2|2019-08-01|
    KR20200116897A|2020-10-13|
    KR102289777B1|2021-08-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR3011683A1|2013-10-03|2015-04-10|Arkema France|PENTACYCLIC ANION SALT: COMPOSITION FOR BATTERIES|CN112448037A|2020-11-30|2021-03-05|广州天赐高新材料股份有限公司|Lithium supplementing composition, lithium supplementing electrolyte and lithium supplementing method for lithium secondary battery|JP3309719B2|1996-07-10|2002-07-29|松下電器産業株式会社|Non-aqueous electrolyte secondary battery|
    CA2199446A1|1997-03-07|1998-09-07|Michel Armand|Polymer electrolyte batteries containing a potassium salt to stabilize performance and operating life|
    USRE37805E1|1997-03-12|2002-07-23|Hydro-Quebec|Polymer electrolyte lithium battery containing a potassium salt|
    KR20160011227A|2006-12-06|2016-01-29|미쓰비시 가가꾸 가부시키가이샤|Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery|
    CN101241774B|2007-02-09|2010-11-10|中国科学院物理研究所|A compound electrolyte composition and its making method|
    JP5273765B2|2007-09-14|2013-08-28|国立大学法人京都大学|Molten salt composition and use thereof|
    US9059481B2|2013-08-30|2015-06-16|Nanotek Instruments, Inc.|Non-flammable quasi-solid electrolyte and non-lithium alkali metal or alkali-ion secondary batteries containing same|
    WO2015132892A1|2014-03-05|2015-09-11|株式会社日立製作所|Electrolyte solution for lithium ion secondary batteries, and lithium ion secondary battery using same|FR3059835B1|2016-12-02|2020-01-24|Arkema France|IMPROVED ION CONDUCTIVITY OF IMIDAZOLATE LITHIUM SALT ELECTROLYTE|
    CN112201855A|2020-10-19|2021-01-08|宁德新能源科技有限公司|Electrolyte solution, electrochemical device, and electronic device|
    法律状态:
    2018-12-13| PLFP| Fee payment|Year of fee payment: 2 |
    2019-08-02| PLSC| Publication of the preliminary search report|Effective date: 20190802 |
    2019-12-16| PLFP| Fee payment|Year of fee payment: 3 |
    2020-12-10| PLFP| Fee payment|Year of fee payment: 4 |
    2021-12-17| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1850664|2018-01-29|
    FR1850664A|FR3077415B1|2018-01-29|2018-01-29|MIXTURE OF LITHIUM AND POTASSIUM SALTS, AND ITS USE IN A BATTERY|FR1850664A| FR3077415B1|2018-01-29|2018-01-29|MIXTURE OF LITHIUM AND POTASSIUM SALTS, AND ITS USE IN A BATTERY|
    JP2020540704A| JP2021511640A|2018-01-29|2019-01-29|Mixtures of potassium and lithium salts and their use in batteries|
    CN201980004302.7A| CN111316493B|2018-01-29|2019-01-29|Mixtures of potassium and lithium salts, and their use in batteries|
    KR1020207002975A| KR102289777B1|2018-01-29|2019-01-29|Mixtures of potassium and lithium salts and their use in batteries|
    US16/637,929| US20200212488A1|2018-01-29|2019-01-29|Mixture of potassium and lithium salts, and use thereof in a battery|
    PCT/FR2019/050196| WO2019145662A2|2018-01-29|2019-01-29|Mixture of potassium and lithium salts, and use thereof in a battery|
    EP19709545.8A| EP3747076A2|2018-01-29|2019-01-29|Mixture of potassium and lithium salts, and use thereof in a battery|
    PL434847A| PL434847A1|2018-01-29|2019-01-29|Mixture of potassium and lithium salts, and use thereof in a battery|
    HU2000261A| HU2000261A1|2018-01-29|2019-01-29|Mixture of potassium and lithium salts, and use thereof in a battery|
    [返回顶部]