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    • 专利摘要:
    The present invention relates to a mixture comprising: lithium bis (fluorosulfonyl) imide; lithium 2-trifluoromethyl-4,5-dicyanoimidazolate; and - lithium hexafluorophosphate; and an electrolyte composition comprising it, and their uses.
    公开号:FR3069959A1
    申请号:FR1757559
    申请日:2017-08-07
    公开日:2019-02-08
    发明作者:Gregory Schmidt
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    MIXTURE OF LITHIUM SALTS AND ITS USE AS A BATTERY ELECTROLYTE
    FIELD OF THE INVENTION
    The present application relates to a mixture of lithium salts, as well as its use as battery electrolyte.
    TECHNICAL BACKGROUND
    A lithium-ion battery or a Li-Souffre 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.
    Among the most used salts are LiPF6 (lithium hexafluorophosphate), which has several of the required qualities, but has the disadvantage of degrading to form hydrofluoric acid (HF) by reaction with water. The HF formed can cause dissolution of the cathode material. The reaction of LiPF6 with residual water therefore affects the longevity of the battery and can cause safety problems, especially in the context of the use of lithium-ion batteries in private vehicles.
    Other salts have therefore been developed, such as lithium LiTFSI (bis (trifluoromethanesulfonyl) imide) and lithium LiFSI (bis (fluorosulfonyl) imide).
    In the field of batteries, there is a constant need for the development of new salts making it possible to improve the performances of the battery, such as the lifetime, and / or the electrochemical stability, and / or the stability on cycling, and / or the reduction in the irreversible capacity of the battery, and / or the performance in power, in particular over a wide temperature range, such as for example from -25 ° C. approximately to 60 ° C. approximately.
    DESCRIPTION OF THE INVENTION
    Mixed
    The present application relates to a mixture comprising (preferably consisting essentially of, and preferably consisting of):
    lithium bis (fluorosulfonyl) imide (LiFSI); lithium 2-trifluoromethyl-4,5-dicyano-imidazolate (LiTDI); and lithium hexafluorophosphate (LiPFe).
    According to one embodiment, the mixture comprises (preferably consisting essentially of, and preferably consisting of):
    from 1% to 98 mol% of bis (fluorosulfonyl) lithium imide (LiFSI);
    from 1% to 98 mol% of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate (LiTDI); and from 1% to 98 mol% of lithium hexafluorophosphate (LiPFe).
    According to the invention, the molar percentages are relative to the total number of moles of the compounds present in the mixture.
    In the context of the invention, the terms “lithium salt of bis (fluorosulfonyl) imide”, “lithium bis (sulfonyl) imide”, “LiFSI”, “LiN (FSC> 2) 2” are used in an equivalent manner. "Bis (sulfonyl) imide lithium", or "lithium bis (fluorosulfonyl) imide".
    In the context of the invention, the “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.
    Lithium 2-trifluoromethyl-4,5-dicyano-imidazolate, 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.
    In the context of the invention, the term "ppm" or "part per million" means ppm by weight.
    Impurities may be present in each LiFSI, LiTDI or LiPF6 salt, for example at a rate of less than 3000 ppm, preferably less than 1000 ppm, in particular less than 500 ppm, for example less than 300 ppm per relative to the total weight of each salt.
    Typically, LiFSI can be obtained according to any known process, for example by the process described in WO2015 / 158979, WO2011 / 065502 or also WO2011 / 149095.
    Typically, LiTDI can be obtained by any known method, for example by the method described in WO2013 / 072591 or WO2010 / 023413.
    Typically, LiPF6 can be obtained according to any known process, for example by the process described in US 3,607,020, US 3,907,977 or also in JP60251109.
    According to one embodiment, the mixture according to the invention comprises:
    at least 5%, preferably at least 10%, preferably at least 15%, even more preferably at least 20%, advantageously at least 25%, and even more advantageously at least 30 mol% of LiFSI; and / or at least 5%, preferably at least 10%, preferably at least 15%, even more preferably at least 20%, and advantageously at least 25 mol% of LiTDI; and / or at least 10%, preferably at least 15%, even more preferably at least 20%, and advantageously at least 25 mol% of LiPF6.
    According to one embodiment, 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%, 10 % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% 65%, 10% to 60%, 10% to 55%, 10% to 50%, 10% to 45%, 15% to 99%, 15% to 95%, 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55 %, from 15% to 50%, from 15% to 45%, from 20% to 99%, from 20% to 95%, from 20% to 90%, from 20% to 85%, from 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 65%, from 20% to 60%, from 20% to 55%, from 20% to 50%, from 20% to 45%, 25% to 99%, 25% to 95%, 25% to 90%, 25% to 85%, 25% to 80%, 25% to 75%, 25% to 70%, 25% to 65%, 25% to 60%, 25% to 55%, 25% to 50%, 25% 45%, 30% to 99%, 30% to 95%, 30% to 90%, 30% to 85%, 30% to 80%, 30% to 75%, 30% to 70%, 30% to 65%, 30% to 60%, 30% to 55%, 30% to 50%, 30% to 45%, 35% to 99%, 35% to 95 %, 35% to 90%, 35% to 85%, 35% to 80%, 35% to 75%, 35% to 70%, 35% to 65%, 35% to 60% , from 35% to 55%, from 35% to
    50%; 40% to 99%, 40% to 95%, 40% to 90%, 40% to 85%, 40% to 80%, 40% to 75%, 40% to 70%, 40% to 65%, 40% to 60%, 40% to 55%, or 40% to 50%.
    According to one embodiment, 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%, 10 % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% 65%, 10% to 60%, 10% to 55%, 10% to 50%, 10% to 45%, 15% to 99%, 15% to 95%, 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55 %, from 15% to 50%, from 15% to 45%, from 20% to 99%, from 20% to 95%, from 20% to 90%, from 20% to 85%, from 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 65%, from 20% to 60%, from 20% to 55%, from 20% to 50%, from 20% to 45%, 25% to 99%, 25% to 95%, 25% to 90%, 25% to 85%, 25% to 80%, 25% to 75%, 25% to 70%, 25% to 65%, 25% to 60%, 25% to 55%, 25% to 50%, 25% 45%, 30% to 99%, 30% to 95%, 30% to 90%, 30% to 85%, 30% to 80%, 30% to 75%, 30% to 70%, 30% to 65%, 30% to 60%, 30% to 55%, 30% to 50%, 30% to 45%, 35% to 99%, 35% to 95 %, 35% to 90%, 35% to 85%, 35% to 80%, 35% to 75%, 35% to 70%, 35% to 65%, 35% to 60% , from 35% to 55%, from 35% to 50%; 40% to 99%, 40% to 95%, 40% to 90%, 40% to 85%, 40% to 80%, 40% to 75%, 40% to 70%, 40% to 65%, 40% to 60%, 40% to 55%, or 40% to 50%.
    According to one embodiment, the content of LiPF6 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%, 10 % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% 65%, 10% to 60%, 10% to 55%, 10% to 50%, 10% to 45%, 15% to 99%, 15% to 95%, 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55 %, from 15% to 50%, from 15% to 45%, from 20% to 99%, from 20% to 95%, from 20% to 90%, from 20% to 85%, from 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 65%, from 20% to 60%, from 20% to 55%, from 20% to 50%, from 20% to 45%, 25% to 99%, 25% to 95%, 25% to 90%, 25% to 85%, 25% to 80%, 25% to 75%, 25% to 70%, 25% to 65%, 25% to 60%, 25% to 55%, 25% to 50%, 25% 45%, 30% to 99%, 30% to 95%, 30% to 90%, 30% to 85%, 30% to 80%, 30% to 75%, 30% to 70%, 30% to 65%, 30% to 60%, 30% to 55%, 30% to 50%, 30% to 45%, 35% to 99%, 35% to 95 %, 35% to 90%, 35% to 85%, 35% to 80%, 35% to 75%, 35% to 70%, 35% to 65%, 35% to 60% , from 35% to 55%, from 35% to
    50%; 40% to 99%, 40% to 95%, 40% to 90%, 40% to 85%, 40% to 80%, 40% to 75%, 40% to 70%, 40% to 65%, 40% to 60%, 40% to 55%, or 40% to 50%.
    According to one embodiment, the above-mentioned mixture comprises (preferably consists essentially of, and preferably consists of):
    from 5% to 90 mol% of LiFSI; from 5% to 90% molar LiTDI; and from 5% to 90 mol% of LiPF6.
    According to one embodiment, the above-mentioned mixture comprises (preferably consists essentially of, and preferably consists of):
    from 20% to 90 mol% of LiFSI; from 5% to 60% molar LiTDI; and from 5% to 60 mol% of LiPF6.
    According to one embodiment, the above-mentioned mixture comprises (preferably consists essentially of, and preferably consists of):
    from 30% to 70 mol% of LiFSI; from 10% to 50% molar LiTDI; and from 10% to 50 mol% of LiPF6.
    According to one embodiment, the above-mentioned mixture comprises (preferably consists essentially of, and preferably consists of):
    from 35% to 60 mol% of LiFSI; from 15% to 50% molar LiTDI; and from 15% to 50 mol% of LiPF6.
    According to one embodiment, the above-mentioned mixture comprises (preferably consists essentially of, and preferably consists of):
    from 35% to 50 mol% of LiFSI; from 20% to 40% molar LiTDI; and from 20% to 40% molar of LiPF6.
    According to one embodiment, the above-mentioned mixture comprises (preferably consists essentially of, and preferably consists of):
    from 35% to 45 mol% of LiFSI; from 25% to 35% molar LiTDI; and from 25% to 35 mol% of LiPF6.
    Preferably, the above-mentioned mixture comprises (preferably consisting essentially of, and preferably consisting of):
    40 mol% LiFSI; 30 mol% LiTDI; and 30 mol% LiPF6.
    Preferably, the above-mentioned mixture comprises (preferably consists essentially of, and preferably consists of):
    50 mol% LiFSI; 20 mol% LiTDI; and 30 mol% LiPF6.
    According to one embodiment, in the mixture according to the invention, the content of LiFSI is greater than or equal to the content of LiTDI, and / or the content of LiPF6 is greater than or equal to LiTDI.
    According to one embodiment, the LiFSI / LiTDI / LiPF6 molar ratio is understood:
    between 1/1/1 and 10/1/1, preferably between 1/1/1 and 5/1/1, preferably between 1/1/1 and 2/1/1. In particular, the LiFSI / LiTDI / LiPF6 molar ratio 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;
    between 1/1/1 and 1/1/10, preferably between 1/1/1 and 1/1/5, preferably between 1/1/1 and 1/1/2;
    between 5/1/3 and 5/4/3, preferably between 5/1/3 and 5/2/3, preferably the molar ratio LiFSI / LiTDI / LiPF 6 is 5/2/3.
    According to one embodiment, the LÎFSI / LÎPF6 molar ratio in the above-mentioned mixture is between 1 and 10, preferably between 1 and 5, preferably between 1 and 2. Preferably, the LiFSI / LiPF6 molar ratio 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 between -30 ° C and 65 ° C, preferably between -25 ° C and 60 ° C, preferably at a temperature greater than or equal to 25 ° C, preferably between 25 ° C and 65 ° C, advantageously between 40 ° C and 60 ° C. 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 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 than LiFSI, LiPF6 and LiTDI. In particular, the electrolyte composition does not include LiTFSI.
    Preferably, the LiFSI, LiPF6 and LiTDI salts represent 100% of all 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 5 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 a preferred embodiment, the molar concentrations of LiFSI, LiTDI and LiPF6 in the electrolyte composition are such that:
    [LiFSI] + [LiTDI] + [LiPFe] s 5 mol / L, preferably <2 mol / L, preferably <1.5 mol / L, even more preferably <1.1 mol / L, for example <1 mol / L
    According to one embodiment, the above-mentioned electrolyte composition comprises:
    - from 0.01 to 0.98 mol / L of LiFSI; from 0.01 to 0.98 mol / L of LiTDI; and from 0.01 to 0.98 mol / L of LiPF6.
    According to one embodiment, 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 even 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, even more preferably at least 0.2 mol / L, advantageously at least 0.25 mol / L, and even more advantageously 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 even more advantageously at least 0.3 mol / L of LiPF6.
    According to one embodiment, 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 0.45 mol / L, 0.15 to 0.99 mol / L, 0.15 to 0.95 mol / L, 0.15 to 0.90 mol / L , 0.15 to 0.85 mol / L, 0.15 to 0.80 mol / L, 0.15 to 0.75 mol / L, 0.15 to 0.70 mol / L, 0.15 to 0.65 mol / L, 0.15 to 0.50 mol / L, 0.15 to 0.45 mol / L, 0.20 to 0.99 mol / L, 0.20 at 0.95 mol / L, from 0.20 to 0.90 mol / L, from 0.20 to 0.85 mol / L, from 0.20 to 0.80 mol / L, from 0.20 to 0 , 75 mol / L, from 0.20 to 0.70 mol / L, from 0.20 0.65 mol / L, 0.20 to 0.50 mol / L, 0.20 to 0.45 mol / L, 0.25 to 0.99 mol / L, 0.25 to 0.95 mol / L, from 0.25 to 0.90 mol / L, from 0.25 to 0.85 mol / L, from 0.25 to 0.80 mol / L, from 0.25 to 0.75 mol / L, from 0.25 to 0.70 mol / L, from 0.25 to 0.65 mol / L, from 0.25 to 0.50 mol / L, from 0.25 to 0.45 mol / L, from 0.30 to 0.99 mol / L, from 0.30 to 0.95 mol / L, from 0.30 to 0.90 mol / L, from 0.30 to 0.85 mol / L, from 0 , 30 to 0.80 mol / L, from 0.30 to 0.75 mol / L, from 0.30 to 0.70 mol / L, from 0.30 to 0.65 mol / L, from 0.30 at 0.50 mol / L, from 0.30 to 0.45 mol / L, from 0.35 to 0.99 mol / L, from 0.35 to 0.95 mol / L, from 0.35 to 0 , 90 mol / L, 0.35 to 0.85 mol / L, 0.35 to 0.80 mol / L, 0.35 to 0.75 mol / L, 0.35 to 0.70 mol / L, 0.35 to 0.65 mol / L, 0.35 to 0.50 mol / L, 0.35 to 0.45 mol / L, 0.40 to 0.99 mol / L, from 0.40 to 0.95 mol / L, from 0.40 to 0.90 mol / L, from 0.40 to 0.85 mol / L, from 0.40 to 0.80 mol / L, from 0.40 to 0.75 mol / L, from 0.40 to 0.75 mol / L, from 0.40 to 0.70 mol / L, from 0.40 to 0.65 mol / L, from 0 , 40 to 0.60 mol / L, from 0.40 to 0.55 mol / L, or from 0.40 to 0.50 mol / L.
    According to one embodiment, 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 0.45 mol / L, 0.15 to 0.99 mol / L, 0.15 to 0.95 mol / L, 0.15 to 0.90 mol / L , 0.15 to 0.85 mol / L, 0.15 to 0.80 mol / L, 0.15 to 0.75 mol / L, 0.15 to 0.70 mol / L, 0.15 to 0.65 mol / L, 0.15 to 0.50 mol / L, 0.15 to 0.45 mol / L, 0.20 to 0.99 mol / L, 0.20 at 0.95 mol / L, from 0.20 to 0.90 mol / L, from 0.20 to 0.85 mol / L, from 0.20 to 0.80 mol / L, from 0.20 to 0 , 75 mol / L, from 0.20 to 0.70 mol / L, from 0.20 0.65 mol / L, 0.20 to 0.50 mol / L, 0.20 to 0.45 mol / L, 0.25 to 0.99 mol / L, 0.25 to 0.95 mol / L, from 0.25 to 0.90 mol / L, from 0.25 to 0.85 mol / L, from 0.25 to 0.80 mol / L, from 0.25 to 0.75 mol / L, from 0.25 to 0.70 mol / L, from 0.25 to 0.65 mol / L, from 0.25 to 0.50 mol / L, from 0.25 to 0.45 mol / L, from 0.30 to 0.99 mol / L, from 0.30 to 0.95 mol / L, from 0.30 to 0.90 mol / L, from 0.30 to 0.85 mol / L, from 0 , 30 to 0.80 mol / L, from 0.30 to 0.75 mol / L, from 0.30 to 0.70 mol / L, from 0.30 to 0.65 mol / L, from 0.30 at 0.50 mol / L, from 0.30 to 0.45 mol / L, from 0.35 to 0.99 mol / L, from 0.35 to 0.95 mol / L, from 0.35 to 0 , 90 mol / L, 0.35 to 0.85 mol / L, 0.35 to 0.80 mol / L, 0.35 to 0.75 mol / L, 0.35 to 0.70 mol / L, 0.35 to 0.65 mol / L, 0.35 to 0.50 mol / L, 0.35 to 0.45 mol / L, 0.40 to 0.99 mol / L, from 0.40 to 0.95 mol / L, from 0.40 to 0.90 mol / L, from 0.40 to 0.85 mol / L, from 0.40 to 0.80 mol / L, from 0.40 to 0.75 mol / L, from 0.40 to 0.75 mol / L, from 0.40 to 0.70 mol / L, from 0.40 to 0.65 mol / L, from 0 , 40 to 0.60 mol / L, from 0.40 to 0.55 mol / L, or from 0.40 to 0.50 mol / L.
    According to one embodiment, 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 0.45 mol / L, 0.15 to 0.99 mol / L, 0.15 to 0.95 mol / L, 0.15 to 0.90 mol / L , 0.15 to 0.85 mol / L, 0.15 to 0.80 mol / L, 0.15 to 0.75 mol / L, 0.15 to 0.70 mol / L, 0.15 to 0.65 mol / L, 0.15 to 0.50 mol / L, 0.15 to 0.45 mol / L, 0.20 to 0.99 mol / L, 0.20 at 0.95 mol / L, from 0.20 to 0.90 mol / L, from 0.20 to 0.85 mol / L, from 0.20 to 0.80 mol / L, from 0.20 to 0 , 75 mol / L, from 0.20 to 0.70 mol / L, from 0.20 0.65 mol / L, 0.20 to 0.50 mol / L, 0.20 to 0.45 mol / L, 0.25 to 0.99 mol / L, 0.25 to 0.95 mol / L, from 0.25 to 0.90 mol / L, from 0.25 to 0.85 mol / L, from 0.25 to 0.80 mol / L, from
    0.25 to 0.75 mol / L, from 0.25 to 0.70 mol / L, from 0.25 to 0.65 mol / L, from 0.25 to 0.50 mol / L, from 0, 25 to 0.45 mol / L, 0.30 to 0.99 mol / L, 0.30 to 0.95 mol / L, 0.30 to 0.90 mol / L, 0.30 to 0.85 mol / L, 0.30 to 0.80 mol / L, 0.30 to 0.75 mol / L, 0.30 to 0.70 mol / L, 0.30 to 0, 65 mol / L, 0.30 to 0.50 mol / L, 0.30 to 0.45 mol / L, 0.35 to 0.99 mol / L, 0.35 to 0.95 mol / L, 0.35 to 0.90 mol / L, 0.35 to 0.85 mol / L, 0.35 to 0.80 mol / L, 0.35 to 0.75 mol / L , 0.35 to 0.70 mol / L, 0.35 to 0.65 mol / L, 0.35 to 0.50 mol / L, 0.35 to 0.45 mol / L, 0.40 to 0.99 mol / L, from 0.40 to 0.95 mol / L, from 0.40 to 0.90 mol / L, from 0.40 to 0.85 mol / L, from 0, 40 to 0.80 mol / L, from 0.40 to 0.75 mol / L, from 0.40 to 0.75 mol / L, from 0.40 to 0.70 mol / L, from 0.40 to 0.65 mol / L, 0.40 to 0.60 mol / L, 0.40 to 0.55 mol / L, or 0.40 to 0.50 mol / L.
    According to one embodiment, the electrolyte composition comprises:
    - from 0.05 to 0.90 mol / L of LiFSI; from 0.05 to 0.90 mol / L of LiTDI; and from 0.05 to 0.90 mol / L of LiPF6.
    According to one embodiment, the electrolyte composition comprises:
    - from 0.2 to 0.90 mol / L of LiFSI; from 0.05 to 0.60 mol / L of LiTDI; and from 0.05 to 0.60 mol / L of LiPF6.
    According to one embodiment, the electrolyte composition comprises:
    - from 0.3 to 0.70 mol / L of LiFSI; 0.1 to 0.50 mol / L of LiTDI; and 0.1 to 0.50 mol / L of LiPF6.
    According to one embodiment, the electrolyte composition comprises:
    - from 0.35 to 0.60 mol / L of LiFSI; 0.15 to 0.50 mol / L of LiTDI; and 0.15 to 0.50 mol / L of LiPF6.
    According to one embodiment, the electrolyte composition comprises:
    - from 0.35 to 0.50 mol / L of LiFSI; from 0.20 to 0.40 mol / L of LiTDI; and
    - from 0.20 to 0.40 mol / L of LiPF 6 .
    According to one embodiment, the electrolyte composition comprises:
    - from 0.35 to 0.45 mol / L of LiFSI;
    from 0.25 to 0.35 mol / L of LiTDI; and from 0.25 to 0.35 mol / L of LiPF6.
    According to one embodiment, the electrolyte composition comprises:
    - 0.40 mol / L of LiFSI;
    - 0.30 mol / L of LiTDI; and
    - 0.30 mol / L of LiPF 6 .
    According to one embodiment, the electrolyte composition comprises:
    - 0.50 mol / L of LiFSI;
    - 0.20 mol / L of LiTDI; and
    - 0.30 mol / L of LiPF 6 .
    According to one embodiment, 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; and or
    - the molar concentration of LiPF 6 is less than or equal to 0.50 mol / L.
    According to one embodiment, the above-mentioned 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.
    According to one embodiment, the above-mentioned electrolyte composition is such that the LiFSI / LiPF6 molar ratio in said composition is between 1/1 and 10/1, preferably between 1/1 and 5/1, preferably between 1 / 1 and 2/1. Preferably, the LiFSI / LiPFe molar ratio in the mixture is 4/3 or 5/3.
    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. Mention may in particular be made 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.
    Preferably, the solvent for the electrolyte composition is ethylene carbonate (EC) / methyl methyl carbonate (EMC) in a volume ratio 3/7.
    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 (C2C> 4) 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 mixtures thereof, 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.
    According to one embodiment, the electrolyte composition according to the invention is chosen from one of the following compositions:
    - i) 0.40 mol / L of LiFSI, 0.30 mol / L of LiTDI, and 0.30 mol / L of LiPF6, fluoroethylene carbonate as an electrolytic additive (in particular at a content less than or equal to 2% by mass relative to the total weight of the solvent (s), mixture of EC / EMC in a 3/7 by volume ratio as solvent;
    ii) 0.50 mol / L of LiFSI, 0.20 mol / L of LiTDI, and 0.30 mol / L of LiPF6, fluoroethylene carbonate as an electrolytic additive (in particular at a content less than or equal to 2% by mass relative to the total weight of the solvent (s), mixture of EC / EMC in a 3/7 by volume ratio as solvent;
    ii) 0.45 mol / L of LiFSI, 0.20 mol / L of LiTDI, and 0.35 mol / L of LiPF6, fluoroethylene carbonate as an electrolytic additive (in particular at a content less than or equal to 2% by mass relative to the total weight of the solvent (s), mixture of EC / EMC in a 3/7 by volume ratio as solvent;
    ii) 0.50 mol / L of LiFSI, 0.10 mol / L of LiTDI, and 0.40 mol / L of LiPF6, fluoroethylene carbonate as an electrolytic additive (in particular at a content less than or equal to 2% by mass relative to the total weight of the solvent (s), mixture of EC / EMC in a ratio 3/7 by volume as solvent.
    According to one embodiment, the electrolyte composition according to the invention is chosen from one of the following compositions:
    - i) 0.40 mol / L of LiFSI, 0.30 mol / L of LiTDI, and 0.30 mol / L of LiPF6, fluoroethylene carbonate as an electrolytic additive (in particular at a content less than or equal to 2% by mass relative to the total weight of the composition), mixture of EC / EMC in a ratio 3/7 by volume as solvent;
    ii) 0.50 mol / L of LiFSI, 0.20 mol / L of LiTDI, and 0.30 mol / L of LiPF6, fluoroethylene carbonate as an electrolytic additive (in particular at a content less than or equal to 2% by mass relative to the total weight of the composition), mixture of EC / EMC in a ratio 3/7 by volume as solvent;
    ii) 0.45 mol / L of LiFSI, 0.20 mol / L of LiTDI, and 0.35 mol / L of LiPF6, fluoroethylene carbonate as an electrolytic additive (in particular at a content less than or equal to 2% by mass relative to the total weight of the composition), mixture of EC / EMC in a ratio 3/7 by volume as solvent;
    ii) 0.50 mol / L of LiFSI, 0.10 mol / L of LiTDI, and 0.40 mol / L of LiPF6, fluoroethylene carbonate as an electrolytic additive (in particular at a content less than or equal to 2% by mass relative to the total weight of the composition), mixture of EC / EMC in a 3/7 by volume ratio as solvent.
    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 Li-ion battery, in particular in a temperature range between -30 ° C and 65 ° C, preferably between - 25 ° C and 60 ° C, preferably at a temperature greater than or equal to 25 ° C, preferably between 25 ° C and 65 ° C, advantageously between 40 ° C and 60 ° C. 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 (MnCh), iron oxide, copper oxide, nickel oxide, oxides lithiummanganese composites (for example LixM ^ CU or LixMnCL), lithium-nickel composition oxides (for example Li x N 1Ο2), lithium-cobalt composition oxides (for example Li x CoO2), lithium-nickel-cobalt composite oxides ( for example LiNii-yCoyCL), 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 (by example Lii + x (NiMnCo) i X C> 2), composite oxides of lithium and transition metal, composite lithium-manganese-nickel oxides with spinel structure (for example LixMn ^ yNiyCU), lithium oxides- phosphorus of olivine structure (for example LixFePCU, Li x Fei-yMn y PO4 or LixCoPCU) , iron sulfate, vanadium oxides, and mixtures thereof.
    Preferably, the positive electrode is comprises an electrochemically active material chosen from LiCoO2, LiFePCU (LFP), LiMn x Co y Ni z O2 (NMC, with x + y + z = 1), LiFePCUF, LiFeSCUF, LiNiCoAICh 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 has good ionic conductivity in solution. In addition, the salt mixture according to the invention advantageously makes it possible to improve the performance in power of the battery, which makes it possible for example to recharge the battery faster, or even to provide the power necessary in the event of an energy peak .
    The salt mixture according to the invention also advantageously makes it possible to have good performance, in particular in terms of power, over a wide temperature range, for example cold, or over a temperature range ranging from approximately -25 ° C. at around 60 ° C.
    The mixture of salts according to the invention advantageously allows a good compromise between a good ionic conductivity in solution, a good lifetime, electrochemical stability, and power performance in particular over a wide temperature range, such as for example from - About 25 ° C to about 60 ° C.
    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
    Abbreviations
    EC: ethylene carbonate
    EMC: methyl methyl carbonate (CAS 623-53-0)
    FEC: fluoroethylene carbonate
    suppliers
    EC: BASF Corporation
    EMC: BASF Corporation
    FEC: BASF Corporation
    LiPFe: BASF Corporation
    The LiFSI used is in particular obtained by the method described in application WO2015 / 158979, while the LiTDI is obtained from the method described in application WO2013 / 072591.
    Example 1: Ionic conductivity measured by impedance spectroscopy
    Two electrolytes were prepared according to the following compositions:
    composition 1 (according to the invention): 0.40M LiFSI, 0.30M LiTDI and 0.30M LiPFe, mixture of EC / EMC solvents 3/7 (volume ratio), 2% by weight in FEC (relative to weight total of EC / EMC solvent mixture);
    composition 2 (comparative): 0.40M LiTFSI, 0.30M LiTDI and 0.30M LiPFe, mixture of EC / EMC solvents 3/7 (volume ratio), 2% by weight in FEC (relative to the total weight of the mixture EC / EMC solvents).
    The compositions were prepared according to the following procedure:
    Composition 1:
    In a glass reactor, 39.60 g of ethylene carbon (30 mL) are dissolved in 70 mL of ethylmethylcarbonate. After obtaining a homogeneous solution, 2.21 g of Fluoroethylene carbonate are added. Then, 4.63 g of LiPF6, 7.60 g of LiFSI and 5.85 g of LiTDI are dissolved in the solution previously obtained.
    Thus, composition 1 comprises LiFSI, LiTDI, LiPF6, EC / EMC (ratio 3/7 by volume), FEC (2% by mass relative to the weight of the solvent EC / EMC 3/7 by 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:
    In a glass reactor, 19.80 g of ethylene carbon (15 mL) are dissolved in 35 mL of ethylmethylcarbonate. After obtaining a homogeneous solution, 1.10 g of Fluoroethylene carbonate are added. Then, 2.31 g of LiPF6, 5.83 g of LiTFSI and 2.92 g of LiTDI are dissolved in the solution previously obtained.
    A conductivity cell is then immersed in each of the solutions and three impedance spectroscopies were carried out. These spectroscopies are performed between 500 mHz and 100 kHz with an amplitude of 10 mV. The cell constant used is 1.12 and the ionic conductivity is calculated according to the following formula:
    σ = -x 1.12 with R represents the resistance which is obtained by linear regression of the curve lm (Z) = f (Re (Z)). In the particular case of lm (Z) = 0, R is equal to the opposite of the intercept divided by the directing coefficient of the linear regression equation.
    compositions Conductivity(MS / cm) R1 R2 R3 R medium Composition 1 (invention) 8.59 129.52 130366 131242 130376 Composition 2(Comparative) 7.18 157.09 155.1567 155.5815 155943
    Composition 1 advantageously has better ionic conductivity than composition 2.
    Example 2: Power test
    A Ragone Plot test was carried out with compositions 1 and 2 prepared in Example 1.
    Method: the method consists in increasing the rate of discharge of a battery in order to observe the capacity of the electrolyte to be able to respond to the stress imposed by the electrical circuit.
    System used:
    Cathode: LiNi0.33Mn0.33Co0.33O2 (89%), VGCF carbon fiber (2.5%), carbon black (2.5%) and 6% Pvdf binder.
    Anode: Lithium metal
    The current was varied between 2.7 and 4.2 V, with the discharges operated in the following order: C / 20, C / 10, C / 5, C / 2, C and 2C.
    Two training cycles at C / 20 are carried out before the study to form all the passivation layers.
    Results:
    The results observed are as follows:
    C rate Composition 1 Composition 2 C / 10 100 100 C / 5 101 101 C / 2 99 98 VS 96 94 2C 91 88 5C 80 76
    The results show that composition 1 advantageously makes it possible to work at higher power regimes than composition 2. These high regimes are particularly sought after in commercial batteries in the context of nomadic devices which always require more power, and electric vehicles which due to their low autonomy require rapid recharges and therefore electrolytes allowing to work at high speeds.
    权利要求:
    Claims (20)
    [1" id="c-fr-0001]
    1. Mixture comprising:
    lithium bis (fluorosulfonyl) imide; lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and lithium hexafluorophosphate.
    [2" id="c-fr-0002]
    2. Mixture according to claim 1 comprising:
    from 1% to 98 mol% of lithium bis (fluorosulfonyl) imide;
    from 1% to 98 mol% of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 1% to 98 mol% of lithium hexafluorophosphate.
    [3" id="c-fr-0003]
    3. Mixture according to claim 1 or claim 2 comprising:
    at least 5%, preferably at least 10%, preferably at least 15%, even more preferably at least 20%, advantageously at least 25%, and even more advantageously at least 30 mol% of lithium bis (fluorosulfonyl) imide; and / or at least 5%, preferably at least 10%, preferably at least 15%, even more preferably at least 20%, and advantageously at least 25 mol% of 2-trifluoromethyl-
    [4" id="c-fr-0004]
    Lithium 4,5-dicyano-imidazolate; and / or at least 10%, preferably at least 15%, even more preferably at least 20%, and advantageously at least 25 mol% of lithium hexafluorophosphate.
    Mixture according to any one of Claims 1 to 3, in which the content of lithium bis (fluorosulfonyl) imide is chosen from one of the following molar percentages: from 1% to 99%, from 1% to 95%, from 5 % to 90%, 5% to 85%, 5% to 80%. from 5% to 75%. from 5% to 70%. from 5% to 65%. from 5% to 50%. from 5% to
    45% of 10% at 99% of 80% of 10% at 75% of 55% of 10% at 50% of 90% of 15% at 85% of 65% of 15% at 60% of 99% of 20% at 95% of 75% of 20% at 70% of 50% of 20% at 45% of 85% of 25% at 80% of
    10% to 95%, 10% to 90%, 10% to 70%, 10% to 65%, 10% to 45%, 15% to 99%, 15% to 80%, 15% to 75 %, 15% to 55%, 15% to 50%, 20% to 90%, 20% to 85%, 20% to 65%, 20% to 60%, 25% to 99%, 25% 95%, 25% to 75%, 25% to 70%, 10% to 85%, 10% to 10% to 60%, 10% to 15% to 95%, 15% to from 15% to 70%, from 15% to from 15% to 45%, from 20% to from 20% to 80%, from 20% to from 20% to 55%, from 20% to from 25% to 90% , from 25% to from 25% to 65%, from 25% to
    60%, 25% to 55%, 25% to 50%, 25% to 45%, 30% to 99%, 30% to
    95%, 30% to 90%, 30% to 85%, 30% to 80%, 30% to 75%, 30% to
    70%, 30% to 65%, 30% to 60%, 30% to 55%, 30% to 50%, 30% to
    45%, 35% to 99%, 35% to 95%, 35% to 90%, 35% to 85%, 35% to
    80%, 35% to 75%, 35% to 70%, 35% to 65%, 35% to 60%, 35% to
    55%, from 35% to 50%; 40% to 99%, 40% to 95%, 40% to 90%, 40% to
    85%, 40% to 80%, 40% to 75%, 40% to 70%, 40% to 65%, 40% to
    60%, from 40% to 55%, or from 40% to 50%; and or
    [5" id="c-fr-0005]
    5. Mixture according to any one of claims 1 to 4, in which the content of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate 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%, from 5% to 80%, from 5% to 75%, from 5% to 70%, from 5% to 65%, from 5% to 50%, 5% to 45%, 10% to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10 % to 75%, 10% to 70%, 10% to 65%, 10% to 60%,
    10% at 55% of 10% at 50% of 10% at 45% of 15% at 99% of 15% at 95% of 15% at 90% of 15% at 85% of 15% at 80% of 15% at 75% of 15% at 70% of 15% at 65% of 15% at 60% of 15% at 55% of 15% at 50% of 15% at 45% of 20% at 99% of 20% at 95% of 20% at 90% of 20% at 85% of 20% at 80% of 20% at 75% of 20% at 70% of 20% at 65% of 20% at 60% of 20% at 55% of 20% at 50% of 20% at 45% of 25% at 99% of 25% at 95% of 25% at 90% of 25% at 85% of 25% at 80% of 25% at 75% of 25% at 70% of 25% at 65% of 25% at 60% of 25% at 55% of 25% at 50% of 25% at 45% of 30% at 99% of 30% at 95% of 30% at 90% of 30% at 85% of 30% at 80% of 30% at 75% of 30% at 70% of 30% at 65% of 30% at 60% of 30% at 55% of 30% at 50% of 30% at 45% of 35% at 99% of 35% at 95% of 35% at 90% of 35% at 85% of 35% at 80% of 35% at 75% of 35% at 70% of 35% at 65% of 35% at 60% of 35% at 55% of 35% at 50%; of 40% at 99% of 40% at 95% of 40% at 90% of 40% at 85% of 40% at 80% of 40% at 75% of 40% at 70% of 40% at 65% of
    40% to 60%, 40% to 55%, or 40% to 50%.
    [6" id="c-fr-0006]
    6. Mixture according to any one of claims 1 to 5, in which the content of lithium hexafluorophosphate is chosen from one of the following molar percentages: from 1% to 99%, from 1% to 95%, from 5% 90%, 5% to 85%, 5% to 80%, 5% to 75%, 5% to 70%, 5% to 65%, 5% to 50%, 5% to 45%, 10% to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70 %, from 10% to 65%, from 10% to 60%, from 10% to
    55%, 10% to 50%, 10% to 45%, 15% to 99%, 15% to 95%, 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%, from 20% to 95%, from 20% to 90%, from 20% to 85%, from 20% to 80%, from 20% to
    75%, from 20% to 70%, from 20% to 65%, from 20% to 60%, from 20% to 55%, from 20% to
    50%, 20% to 45%, 25% to 99%, 25% to 95%, 25% to 90%, 25% to
    85%, 25% to 80%, 25% to 75%, 25% to 70%, 25% to 65%, 25% to
    60%, 25% to 55%, 25% to 50%, 25% to 45%, 30% to 99%, 30% to
    95%, 30% to 90%, 30% to 85%, 30% to 80%, 30% to 75%, 30% to
    70%, 30% to 65%, 30% to 60%, 30% to 55%, 30% to 50%, 30% to
    45%, 35% to 99%, 35% to 95%, 35% to 90%, 35% to 85%, 35% to
    80%, 35% to 75%, 35% to 70%, 35% to 65%, 35% to 60%, 35% to
    55%, from 35% to 50%; 40% to 99%, 40% to 95%, 40% to 90%, 40% to
    85%, 40% to 80%, 40% to 75%, 40% to 70%, 40% to 65%, 40% to
    60%, from 40% to 55%, or from 40% to 50%.
    [7" id="c-fr-0007]
    7. Mixture according to any one of claims 1 to 6, comprising:
    i) from 5% to 90 mol% of lithium bis (fluorosulfonyl) imide;
    from 5% to 90 mol% molar 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 5% to 90 mol% of lithium hexafluorophosphate;
    or
    Ii) from 20% to 90 mol% of lithium bis (fluorosulfonyl) imide;
    from 5% to 60% molar 2-trifluoromethyl-4,5-dicyano-imidazolate lithium; and from 5% to 60 mol% of lithium hexafluorophosphate;
    Or iii) from 30% to 70 mol% of lithium bis (fluorosulfonyl) imide;
    from 10% to 50 mol% lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 10% to 50 mol% of lithium hexafluorophosphate;
    or iv) from 35% to 60 mol% of lithium bis (fluorosulfonyl) imide;
    from 15% to 50 mol% lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 15% to 50 mol% of lithium hexafluorophosphate;
    or
    v) from 35% to 50 mol% of lithium bis (fluorosulfonyl) imide;
    from 20% to 40 mol% lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 20% to 40 mol% of lithium hexafluorophosphate;
    or vi) from 35% to 45 mol% of lithium bis (fluorosulfonyl) imide;
    from 25% to 35 mol% lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 25% to 35 mol% of lithium hexafluorophosphate;
    or vii) 40 mol% of lithium bis (fluorosulfonyl) imide;
    30 mol% 2-trifluoromethyl-4,5-dicyano-imidazolate lithium; and 30 mol% of lithium hexafluorophosphate;
    or viii) 50 mol% of lithium bis (fluorosulfonyl) imide;
    20 mol% 2-trifluoromethyl-4,5-dicyano-imidazolate lithium; and 30 mol% of lithium hexafluorophosphate.
    [8" id="c-fr-0008]
    8. Mixture according to any one of claims 1 to 7, in which the molar ratio bis (fluorosulfonyl) lithium imide / lithium hexafluorophosphate is between 1/1 and 10/1, preferably between 1/1 and 5 / 1, preferably between 1/1 and 2/1, the molar ratio bis (fluorosulfonyl) lithium imide / lithium hexafluorophosphate being in particular 4/3 or 5/3.
    [9" id="c-fr-0009]
    9. An electrolyte composition comprising the mixture of lithium salts as defined according to any one of claims 1 to 8, at least one solvent, and optionally at least one electrolytic additive.
    [10" id="c-fr-0010]
    10. Composition according to claim 9, in which the lithium bis (fluorosulfonyl) imide salts, lithium hexafluorophosphate and lithium 2trifluoromethyl-4,5-dicyano-imidazolate represent 100% of all the salts present in the composition.
    [11" id="c-fr-0011]
    11. Composition according to any one of claims 9 or 10, in which the molar concentration of the mixture 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, preferably less than or equal to 1.5 mol / L, in particular less than or equal to 1.1 mol / L, for example less than or equal to 1 mol / L.
    [12" id="c-fr-0012]
    12. Composition according to any one of claims 9 to 11, comprising:
    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 even more advantageously at least 0.3 mol / L of bis (fluorosulfonyl) lithium imide; 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 even more advantageously at least 0.3 mol / L of lithium 2trifluoromethyl-4,5-dicyano-imidazolate; 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 even more advantageously at least 0.3 mol / L of lithium hexafluorophosphate.
    [13" id="c-fr-0013]
    13. Composition according to any one of claims 9 to 12, comprising: i) from 0.05 to 0.90 mol / L of lithium bis (fluorosulfonyl) imide;
    from 0.05 to 0.90 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 0.05 to 0.90 mol / L of lithium hexafluorophosphate.
    or
    ü) from 0.2 to 0.90 mol / L of bis (fluorosulfonyl) lithium imide;
    from 0.05 to 0.60 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 0.05 to 0.60 mol / L of lithium hexafluorophosphate.
    or iü) from 0.3 to 0.70 mol / L of lithium bis (fluorosulfonyl) imide;
    0.1 to 0.50 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and 0.1 to 0.50 mol / L of lithium hexafluorophosphate.
    or iv) from 0.35 to 0.60 mol / L of lithium bis (fluorosulfonyl) imide;
    0.15 to 0.50 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and 0.15 to 0.50 mol / L of lithium hexafluorophosphate.
    or
    v) from 0.35 to 0.50 mol / L of lithium bis (fluorosulfonyl) imide;
    from 0.20 to 0.40 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 0.20 to 0.40 mol / L of lithium hexafluorophosphate.
    or vi) from 0.35 to 0.45 mol / L of lithium bis (fluorosulfonyl) imide;
    from 0.25 to 0.35 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and from 0.25 to 0.35 mol / L of lithium hexafluorophosphate.
    or vii)
    0.40 mol / L of lithium bis (fluorosulfonyl) imide;
    0.30 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and 0.30 mol / L of lithium hexafluorophosphate.
    or viii)
    0.50 mol / L of lithium bis (fluorosulfonyl) imide;
    0.20 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate; and 0.30 mol / L of lithium hexafluorophosphate.
    [14" id="c-fr-0014]
    14. Composition according to any one of claims 9 to 13, in which the solvent is chosen from the group consisting of ethers, carbonates, esters, ketones, partially hydrogenated hydrocarbons, nitriles, amides, alcohols, sulfoxides, sulfolane, nitromethane, 1,3-dimethyl-2imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1, H) -pyrimidinone, 3methyl- 2-oxazolidinone, and mixtures thereof.
    [15" id="c-fr-0015]
    15. Composition according to any one of claims 9 to 14, in which the solvent is chosen from carbonates and their mixtures, for example from the following mixtures:
    ethylene carbonate / propylene carbonate / dimethyl carbonate in a 1/1/1 mass ratio;
    ethylene carbonate / propylene carbonate / diethyl carbonate in a 1/1/1 mass ratio;
    ethylene carbonate / propylene carbonate / methyl ethyl carbonate in a 1/1/1 mass ratio;
    ethylene carbonate / dimethyl carbonate in a mass ratio 1/1; ethylene carbonate / diethyl carbonate in a 1/1 mass ratio; ethylene carbonate / methyl ethyl carbonate in a 1/1 mass ratio; ethylene carbonate / dimethyl carbonate in a mass ratio in a volume ratio 3/7;
    ethylene carbonate / diethyl carbonate in a volume ratio 3/7; ethylene carbonate / methyl methyl carbonate in a volume ratio 3/7; the solvent preferably being ethylene carbonate / methyl ethyl carbonate in a volume ratio 3/7.
    [16" id="c-fr-0016]
    16. Composition according to any one of claims 9 to 15, in which the electrolytic additive is chosen from the group consisting of fluoroethylene carbonate, vinylene carbonate, 4-vinyl-1,3-dioxolan-2-one, pyridazine, vinyl pyridazine, quinoline, vinyl quinoline, butadiene, sebaconitrile, LiB (C2C> 4) 2, lithium nitrate, alkyldisulfide, fluorotoluene, 1,4-dimethoxytetrafluorotoluene , t-butylphenol, di-t-butyphenol, 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 fluorinated carbonate thylène.
    [17" id="c-fr-0017]
    17. Composition according to any one of claims 9 to 16, chosen from one of the following compositions:
    i) 0.40 mol / L of bis (fluorosulfonyl) lithium imide, 0.30 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate, and 0.30 mol / L of LiPF6, fluoroethylene carbonate as electrolytic additive in particular at a content less than or equal to 2% by mass, ethylene carbonate / methyl ethyl carbonate mixture in a 3/7 by volume ratio as solvent;
    ii) 0.50 mol / L of lithium bis (fluorosulfonyl) imide, 0.20 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate, and 0.30 mol / L of LiPF6, fluoroethylene carbonate as electrolytic additive in particular at a content less than or equal to 2% by mass, ethylene carbonate / methyl ethyl carbonate mixture in a 3/7 by volume ratio as solvent;
    ii) 0.45 mol / L of lithium bis (fluorosulfonyl) imide, 0.20 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate, and 0.35 mol / L of LiPF6, fluoroethylene carbonate as electrolytic additive in particular at a content less than or equal to 2% by mass, ethylene carbonate / methyl ethyl carbonate mixture in a 3/7 by volume ratio as solvent;
    ii) 0.50 mol / L of bis (fluorosulfonyl) lithium imide, 0.10 mol / L of lithium 2-trifluoromethyl-4,5-dicyano-imidazolate, and 0.40 mol / L of LiPF6, fluoroethylene carbonate as electrolytic additive in particular at a content less than or equal to 2% by mass, ethylene carbonate / methyl methyl carbonate mixture in a 3/7 by volume ratio as solvent.
    [18" id="c-fr-0018]
    18. Use of a mixture according to any one of claims 1 to 8, or of an electrolyte composition according to any one of claims 9 to 17, in a Li-ion battery, in particular in a range of temperature between -30 ° C and 65 ° C, preferably between -25 ° C and 60 ° C, preferably at a temperature greater than or equal to 25 ° C, preferably between 25 ° C and 65 ° C, advantageously between 40 ° C and 60 ° C.
    [19" id="c-fr-0019]
    19. Electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte composition according to any one of claims 9 to 17, interposed between the negative electrode and the positive electrode, or a mixture as defined according to l any of claims 1 to 8.
    [20" id="c-fr-0020]
    20. Battery comprising at least one electrochemical cell according to claim
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    同族专利:
    公开号 | 公开日
    JP2020529425A|2020-10-08|
    FR3069959B1|2019-08-23|
    CN110998950A|2020-04-10|
    WO2019030440A1|2019-02-14|
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    US3907977A|1969-05-29|1975-09-23|United States Steel Corp|Method for the preparation of high purity, highly surface active LiAsF{HD 6|
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    FR3020060B1|2014-04-18|2016-04-01|Arkema France|PREPARATION OF IMIDES CONTAINING FLUOROSULFONYL GROUP|FR3096512B1|2019-05-22|2021-11-05|Arkema France|ELECTROLYTE BASED ON LITHIUM SALTS|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1757559A|FR3069959B1|2017-08-07|2017-08-07|MIXTURE OF LITHIUM SALTS AND USES THEREOF AS BATTERY ELECTROLYTE|
    FR1757559|2017-08-07|FR1757559A| FR3069959B1|2017-08-07|2017-08-07|MIXTURE OF LITHIUM SALTS AND USES THEREOF AS BATTERY ELECTROLYTE|
    EP18758933.8A| EP3665737A1|2017-08-07|2018-07-26|Lithium salt mixture and uses thereof as a battery electrolyte|
    US16/630,223| US20210151798A1|2017-08-07|2018-07-26|Lithium salt mixture and uses thereof as a battery electrolyte|
    JP2020505495A| JP2020529425A|2017-08-07|2018-07-26|Lithium salt mixture and its use as a battery electrolyte|
    PCT/FR2018/051912| WO2019030440A1|2017-08-07|2018-07-26|Lithium salt mixture and uses thereof as a battery electrolyte|
    CN201880050215.0A| CN110998950A|2017-08-07|2018-07-26|Lithium salt mixtures and their use as battery electrolytes|
    KR1020207001430A| KR20200038927A|2017-08-07|2018-07-26|Lithium salt mixture and its use as battery electrolyte|
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