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    • 专利摘要:
    The present invention relates to a process for drying and purifying a bis (fluorosulfonyl) imide lithium salt in solution in an organic solvent S1, said process comprising the following steps: a) adding deionized water to dissolve and extract the salt bis (fluorosulfonyl) imide lithium, forming an aqueous solution of said salt; b) extracting the bis (fluorosulfonyl) imide lithium salt from said aqueous solution with an organic solvent S 2, this step being repeated at least once; c) concentration of the bis (fluorosulfonyl) imide lithium salt by evaporation of said organic solvent S2 and water, in a short-path thin film evaporator, under the following conditions: - temperature between 30 ° C and 95 ° C; pressure between 10-3 mbar abs and 5 mbar abs; - residence time less than or equal to 15 min; d) optionally crystallization of the lithium salt of bis (fluorosulfonyl) imide. The present invention also relates to a bis (fluorosulfonyl) imide lithium salt, and its uses in Li-ion batteries.
    公开号:FR3059994A1
    申请号:FR1662130
    申请日:2016-12-08
    公开日:2018-06-15
    发明作者:Gregory Schmidt；Remy Teissier
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    (54) METHOD FOR DRYING AND PURIFYING LIFSI.
    The present invention relates to a method for drying and purifying a lithium salt of bis (fluorosulfonyl) imide in solution in an organic solvent S1, said method comprising the following steps:
    a) addition of deionized water to dissolve and extract the lithium salt of bis (fluorosulfonyl) imide, forming an aqueous solution of said salt;
    b) extraction of the lithium salt of bis (fluorosulfonyl) imide from said aqueous solution, with an organic solvent S2, this step being repeated at least once;
    c) concentration of the lithium salt of bis (fluorosulfonyl) imide by evaporation of said organic solvent S2 and of water, in a thin film evaporator with a short path, under the following conditions:
    - temperature between 30 ° C and 95 ° C;
    - pressure between 10-3 mbar abs and 5 mbar abs;
    - residence time less than or equal to 15 min;
    d) optionally crystallization of the lithium salt of bis (fluorosulfonyl) imide.
    The present invention also relates to a lithium salt of bis (fluorosuIfonyl) imide, and its uses in Li-ion batteries.
    ι
    LiFSI drying and purification process
    FIELD OF THE INVENTION
    The present invention relates to the field of Li-ion batteries. More particularly, the invention relates to a process for drying and purifying a lithium salt of bis (fluorosulfonyl) imide.
    The invention also relates to a process for the manufacture of a lithium salt of bis (fluorosulfonyl) imide, dried and purified by the drying and purification process according to the invention. The present invention also relates to a lithium salt of bis (fluorosulfonyl) imide comprising a reduced content of water and of sulfates, and its various uses.
    The Li-ion battery market requires the development of higher power batteries. This involves increasing the nominal voltage of Li-ion batteries. To achieve the target voltages, high purity electrolytes are required. The sulfonylimide anions, by their very low basicity, are increasingly used in the field of energy storage in the form of inorganic salts in batteries, or organic salts in super capacitors or in the field of liquids ionic.
    In the specific field of Li-ion batteries, the salt currently most used is LiPF6. This salt shows many disadvantages such as limited thermal stability, sensitivity to hydrolysis and therefore lower battery security. Recently, new salts with the fluorosulfonyl FSCh ”group have been studied and have demonstrated numerous advantages such as better ionic conductivity and resistance to hydrolysis. One of these salts, LiFSI, has shown very interesting properties which make it a good candidate to replace LiPF6.
    The identification and quantification of impurities in salts and / or electrolytes, and the understanding of their impacts on battery performance become essential. For example, impurities with a mobile proton, due to their interference with electrochemical reactions, lead to lower overall performance and stability of Li-ion batteries. The application of Li-ion batteries requires having high purity products (minimum of impurities and in particular having a very low residual humidity).
    Document US 9079780 describes different methods of concentrating
    LiFSI, to remedy the formation of by-products:
    - drying under a current of inert and dry gas;
    and or
    - concentration of a LiFSI solution via a thin film evaporator.
    The examples in this document describe obtaining LiFSI with high water and sulphate contents. Such salts in particular have drawbacks such as corrosion problems of the current collector, safety, etc.
    There is a need for a new method for drying a lithium salt of bis (fluorosulfonyl) imide, making it possible in particular to obtain said salt with a reduced content of residual water and of sulfates.
    There is also a need for new LiFSI compositions which do not have the drawbacks of known LiFSI salts, which are in particular compatible with applications in electronics, such as Li-ion batteries.
    DESCRIPTION OF THE INVENTION
    According to a first aspect, the invention relates to a process for drying and purifying a lithium salt of bis (fluorosulfonyl) imide in solution in an organic solvent S1, said process comprising the following steps:
    a) addition of deionized water to dissolve and extract the lithium salt of bis (fluorosulfonyl) imide, forming an aqueous solution of said salt;
    a ’) possible concentration of said aqueous solution of said salt;
    b) extraction of the lithium salt of bis (fluorosulfonyl) imide from said aqueous solution, with an organic solvent S2, preferably said solvent S2 forming an azeotropic mixture with water, this step being repeated at least once;
    c) concentration of the lithium salt of bis (fluorosulfonyl) imide by evaporation of said organic solvent S2 and of water, in a short-film thin film evaporator, under the following conditions:
    - temperature between 30 ° C and 95 ° C, preferably between 30 ° C and
    90 ° C, preferably between 40 ° C and 85 ° C;
    - pressure between 10 ' 3 mbar abs and 5 mbar abs;
    - residence time less than or equal to 15 min, preferably less than or equal to 10 min, and advantageously less than or equal to 5 min;
    d) optionally crystallization of the lithium salt of bis (fluorosulfonyl) imide.
    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 term "ppm" means ppm by weight.
    For example, the term "salt having a water content less than or equal to 40 ppm by weight" means a salt having a water content less than or equal to 40 ppm by weight relative to the total weight of said salt.
    The initial solution of bis (fluorosulfonyl) imide lithium salt may come from any synthesis of the lithium salt of bis (fluorosulfonyl) imide, comprising in particular the following steps:
    i) synthesis of bis (chlorosulfonyl) imide;
    ii) fluorination of bis (chlorosulfonyl) imide to bis (fluorosulfonyl) imide;
    iii) preparation of an alkaline or alkaline earth salt of bis (fluorosulfonyl) imide by neutralization of bis (fluorosulfonyl) imide;
    iv) cation exchange to obtain the lithium salt of the bis (fluorosulfonyl) imide.
    At the end of these steps, the lithium salt of the bis (fluorosulfonyl) imide is preferably obtained in solution in an organic solvent (corresponding in particular to solvent S1), at a mass concentration of between 5% and 50% by mass relative to the total mass of the solution.
    Such a method is for example described in document WO 2015/158979.
    According to one embodiment, the above-mentioned organic solvent S1 is chosen from the group consisting of esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and their mixtures. Preferably, the solvent S1 is chosen from dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran, acetronitrile, diethyl ether, and their mixtures. Preferably, the organic solvent S1 is butyl acetate.
    According to the invention, the organic solvent S1 and the organic solvent S2 can be the same or different.
    Preferably, the organic solvent S1 and the organic solvent S2 are identical.
    According to one embodiment, the mass content of LiFSI in the organic solvent S1 is between 5% and 55%, preferably between 5% and 50%, preferably between 10% and 55%, advantageously between 10% and 50%, for example between 10% and 40%, in particular between 15% and 40%, and preferably between 25% and 35% by mass, relative to the total mass of the solution.
    According to one embodiment, step a), of the purification and drying method according to the invention, comprises the addition of deionized water to the solution of LiFSI in the above-mentioned organic solvent S1, for example obtained during steps previous synthesis, to allow the dissolution of said salt, and the extraction of said salt in water (aqueous phase).
    The extraction can be carried out by any known extraction means.
    The drying and purification process of the invention can include one or more extractions with deionized water, for example three. In a first extraction, an amount of deionized water corresponding to half the mass of the initial solution can be added, then an amount equal to approximately 1/3 of the mass of the initial solution during the second extraction, then a amount equal to approximately 1/4 of the mass of the initial solution during the third extraction.
    In the case of multiple extractions, the aqueous phases extracted can be combined together to form a single aqueous solution.
    At the end of step a), an aqueous LiFSI solution is obtained in particular.
    According to one embodiment, the mass content of LiFSI in the aqueous solution is between 5% and 35%, preferably between 10% and 25%, relative to the total mass of the solution.
    The method according to the invention may comprise a concentration step a ') between step a) and step b), preferably to obtain an aqueous LiFSI solution comprising a mass content of LiFSI of between 20% and 80% , in particular between 25% and 80%, preferably between 25% and 70%, and advantageously between 30% and 65% relative to the total mass of the solution. The concentration step can be carried out by a rotary evaporator under reduced pressure, at a pressure below 50 mbar abs (preferably less than 30 mbar abs), and in particular at a temperature between 25 ° C and 60 ° C, for example at 40 ° C.
    Preferably, the drying and purification process according to the invention comprises step a ’). After concentration a ’) of the aqueous solution obtained at the end of step a), a concentrated aqueous solution of LiFSI is obtained.
    The LiFSI, contained in the aqueous solution obtained at the end of step a), and of a possible concentration step, can then be recovered by extraction with an organic solvent S2, said solvent S2 can preferably form an azeotrope with water (step b). Step b) of the method according to the invention leads in particular, after extraction, to an organic phase, saturated with water, containing LiFSI (it is a solution of LiFSI in organic solvent S2, said solution being saturated with water).
    The extraction solvent S2 of the LiFSI salt dissolved in deionized water is advantageously:
    • a good solvent for the LiFSI salt, that is to say that the LiFSI can have a solubility greater than or equal to 10% by weight relative to the total weight of the sum LiFSI and solvent; and / or • poorly soluble in water, that is to say that it has a solubility less than or equal to 1% by weight relative to the total weight of the sum of solvent and water.
    According to one embodiment, the organic solvent S2 is chosen from the group consisting of esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and their mixtures. Preferably, the solvent S2 is chosen from ethers, esters and their mixtures. For example, mention may be made of methyl t-butyl ether, cyclopentyl methyl ether, ethyl acetate, propyl acetate, butyl acetate. Dichloromethane, tetrahydrofuran, acetronitrile, diethyl ether, and their mixtures. Preferably, the solvent S2 is chosen from methyl-t-butyl ether, cyclopentylmethyl ether, ethyl acetate, propyl acetate, butyl acetate, and their mixtures.
    Preferably, the organic solvent is butyl acetate.
    Extraction step b) is repeated at least once, preferably from one to ten times, and in particular four times. The organic phases can then be combined into one before step c).
    For each extraction, the mass quantity of organic solvent S2 used can vary between 1/6 and 1 times the mass of the aqueous phase. Preferably, the mass ratio of organic solvent S2 / water, during an extraction of step b), varies from 1/6 to 1/1, the number of extractions varying in particular from 2 to 10.
    According to one embodiment, the mass content of LiFSI in solution in the organic phase is between 5% and 35%, preferably between 10% and 25% by mass relative to the total mass of the solution.
    The process can comprise a concentration step between step b) and step c), preferably to obtain a solution of LiFSI in organic solvent S2 comprising a mass content of LiFSI of between 20% and 60%, and preferably between 30% and 50% by mass relative to the total mass of the solution. The concentration step can be carried out by a rotary evaporator under reduced pressure, in particular at 40 ° C. and at a pressure below 30 mbar abs.
    According to one embodiment, step c) of the method according to the invention consists in the concentration of the LiFSI solution in the organic solvent S2 (obtained in particular at the end of step b)).
    According to the invention, step c) of concentration can be carried out at a pressure between 10 ' 2 mbar abs and 5 mbar abs, preferably between 5.10' 2 mbar abs and 2 mbar abs, preferably between 0.1 and 1 mbar abs, and in particular between 0.4 and 0.6 mbar abs. In particular, step c) is carried out at 0.5 mbar abs.
    According to one embodiment, step c) is carried out at a temperature between 30 ° C and 95 ° C, preferably between 30 ° C and 90 ° C, preferably between 40 ° C and 85 ° C, and in particular between 60 ° C and 80 ° C, preferably at 80 ° C.
    According to one embodiment, step c) is carried out with a residence time less than or equal to 15 min, preferably less than 10 min and preferably less than or equal to 5 minutes and advantageously less than or equal to 3 minutes.
    In the context of the invention, and unless otherwise stated, the term "residence time" means the time which elapses between the entry of the solution of lithium salt of bis (fluorosulfonyl) imide (in particular obtained at after step b) above) in the evaporator and the outlet of the first drop of the solution.
    According to a preferred embodiment, the temperature of the condenser of the thin-film evaporator with short path is between -50 ° C and 5 ° C, preferably between -35 ° C and 5 ° C. In particular, the condenser temperature is -5 ° C.
    The short-path thin film evaporators according to the invention are also known under the name "Wiped film short path" (WFSP). They are typically called so because the vapors generated during evaporation make a "short path" (short distance) before being condensed in the condenser.
    Among the short path scraped evaporators, we can notably mention the evaporators marketed by the companies Buss SMS Ganzler ex Luwa AG, LUC Gmbh or VTA Process.
    Typically, short-path thin film evaporators can include a solvent vapor condenser placed inside the device itself (especially in the center of the device), unlike other types of film evaporator in which the condenser is located outside the device.
    In this type of device, the formation of a thin film of product to be distilled on the internal hot wall of the evaporator can typically be ensured by continuous spreading over the evaporation surface using mechanical means. detailed below.
    The evaporator can in particular be provided at its center with an axial rotor on which are mounted the mechanical means which allow the film to form on the wall. They may be rotors fitted with fixed blades: lobed rotors with three or four blades made of flexible or rigid materials, distributed over the entire height of the rotor, or rotors fitted with movable blades, paddles, scraper blades, guided wipers. In this case, the rotor can be constituted by a succession of pallets articulated on a pivot mounted on a shaft or axis by means of radial supports. Other rotors can be fitted with mobile rollers mounted on secondary axes and said rollers are pressed onto the wall by centrifugation. The rotational speed of the rotor, which depends on the size of the device, can be easily determined by a person skilled in the art. The different mobiles can be made of various materials, metallic for example steel, alloy steel (stainless steel), aluminum, or polymeric, for example polytetrafluroethylene PTFE or glass materials (enamel); metallic materials coated with polymeric materials.
    According to one embodiment, the LiFSI salt solution is introduced into the short-film thin film evaporator with a flow rate of between 700g / h and 1200g / h, preferably between 900g / h and 1100g / h for a surface 0.04m 2 evaporation.
    The process according to the invention advantageously makes it possible to obtain a LiFSI salt having in particular a water content less than or equal to 45 ppm by weight, preferably less than or equal to 40 ppm by weight, and in particular a lower sulphate content or equal to 100 ppm, preferably less than or equal to 50 ppm. The method according to the invention advantageously makes it possible to obtain a LiFSI salt compatible with the applications in electrolytes for Li-ion batteries.
    According to the invention, at the end of step c) above, the LiFSI can be obtained in solid form, and in particular in crystallized form, or in the form of a concentrated solution, said concentrated solution comprising less than 10% by weight of residual solvent relative to the total weight of said concentrated solution.
    According to one embodiment, the method according to the invention further comprises a step d) of crystallization of the lithium salt of the bis (fluorosulfonyl) imide obtained at the end of step c) above.
    Preferably, during step d), the LiFSI is crystallized when cold, in particular at a temperature less than or equal to 25 ° C.
    Preferably, the crystallization step d) of LiFSI is carried out in an organic solvent S3 ("crystallization solvent") chosen from chlorinated solvents, such as for example dichloromethane, and aromatic solvents, such as for example toluene , in particular at a temperature less than or equal to 25 ° C. Preferably, the LiFSI crystallized at the end of step d) is recovered by filtration.
    According to one embodiment, the method for drying and purifying a lithium salt of the bis (fluorosulfonyl) imide in solution in an organic solvent S1, according to the invention, comprises the following four steps:
    a) adding deionized water to the LiFSI solution in an organic solvent S1, allowing the extraction of the LiFSI salt in water;
    a ’) possible concentration of said aqueous solution of said salt;
    b) extraction of the LiFSI salt using an organic solvent S2 preferably forming an azeotropic mixture with water;
    c) concentration of LiFSI by evaporation of said organic solvent S2, in particular resulting in water with the solvent; and
    d) crystallization of the bis (fluorosulfonyl) imide salt.
    According to one embodiment, the drying and purification process according to the invention comprises the following steps:
    a) addition of deionized water to the solution of LiFSI in organic solvent S1, in particular in butyl acetate, to dissolve and extract the lithium salt of bis (fluorosulfonyl) imide, forming an aqueous solution of said salt, the content mass by LiFSI in organic solvent S1 being in particular between 5% and 55%;
    a ’) optional concentration of the solution obtained at the end of step a), to obtain an aqueous LiFSI solution having a LiFSI content of between 20 and 80%, preferably between 30% and 65%;
    b) extraction of the lithium salt of bis (fluorosulfonyl) imide from said aqueous solution, with an organic solvent S2 preferably forming an azeotropic mixture with water, this step being repeated at least once;
    c) concentration of the lithium salt of bis (fluorosulfonyl) imide by evaporation of said organic solvent S2 and of water, in a short-film thin film evaporator, under the following conditions:
    - temperature between 30 ° C and 95 ° C, preferably between 30 ° C and
    90 ° C, preferably between 40 ° C and 85 ° C, and in particular at 80 ° C;
    - pressure between 10 ' 3 mbar abs and 5 mbar abs, and in particular at
    0.5 mbar abs;
    - residence time less than or equal to 15 min, preferably less than or equal to 5 min, preferably less than or equal to 3 min;
    c) crystallization of the lithium salt of the bis (fluorosulfonyl) imide in an organic solvent S3 chosen from chlorinated solvents, such as for example dichloromethane, and aromatic solvents, such as for example toluene, at a temperature less than or equal to 25 ° C.
    filtration) to recover the LiFSI.
    According to one embodiment, the drying and purification process according to the invention comprises the following steps:
    a) addition of deionized water to the solution of LiFSI in organic solvent S1, in particular in butyl acetate, to dissolve and extract the lithium salt of bis (fluorosulfonyl) imide, forming an aqueous solution of said salt, the content mass by LiFSI in organic solvent S1 being in particular between 5% and 55%;
    a ') concentration of the solution obtained at the end of step a), to obtain an aqueous LiFSI solution having a LiFSI content of between 20 and 80%, preferably between 30% and 65%, preferably with a temperature of 40 ° C and at a pressure less than or equal to 50 mbar abs;
    b) extraction of the lithium salt of bis (fluorosulfonyl) imide from said aqueous solution, with an organic solvent S2 preferably forming an azeotropic mixture with water, this step being repeated at least once;
    c) concentration of the lithium salt of bis (fluorosulfonyl) imide by evaporation of said organic solvent S2 and of water, in a short-film thin film evaporator, under the following conditions:
    - temperature between 30 ° C and 95 ° C, preferably between 30 ° C and
    90 ° C, preferably between 40 ° C and 85 ° C, and in particular at 80 ° C;
    - pressure between 10 ' 3 mbar abs and 5 mbar abs, and in particular at
    0.5 mbar abs;
    - residence time less than or equal to 15 min, preferably less than or equal to 5 min, preferably less than or equal to 3 min;
    d) crystallization of the lithium salt of the bis (fluorosulfonyl) imide in an organic solvent S3 chosen from chlorinated solvents, such as for example dichloromethane, and aromatic solvents, such as for example toluene, at a temperature less than or equal to 25 ° C.
    filtration) to recover the LiFSI.
    The method according to the invention advantageously makes it possible to obtain LiFSI comprising a water content less than or equal to 45 ppm, in particular less than or equal to 40 ppm by mass relative to the total mass of said LiFSI.
    Preferably, the method according to the invention leads to a LiFSI comprising a mass proportion of water of for example between 5 and 45 ppm, between 8 and 45 ppm, between 9 and 45 ppm, between 10 and 45 ppm, between 12 and 45 ppm, between 15 and 45 ppm, between 20 and 45 ppm, between 25 and 45 ppm, between 30 and 45 ppm, between 5 and 40, between 8 and 40 ppm, between and 40, between 10 and 40 ppm, between 12 and 40 ppm, between 15 and 40 ppm, between 20 and 40 ppm, ίο between 25 and 40 ppm, or between 30 and 40 ppm by mass relative to the total mass of said salt.
    Preferably, the process according to the invention leads to a LiFSI salt whose mass proportion in sulfate ions is for example less than or equal to 100 ppm, less than or equal to 90 ppm, less than or equal to 80 ppm, less than or equal to 70 ppm, less than or equal to 60 ppm, less than or equal to 50 ppm, less than or equal to 40 ppm, or less than or equal to 30 ppm, less than or equal to 20 ppm, less than or equal to 15 ppm, or less or equal at 10 ppm by mass relative to the total mass of said salt.
    Preferably, the method according to the invention leads to a LiFSI salt comprising a mass proportion of sulphate ions for example between 2 and 100 ppm, between 2 and 90 ppm, between 2 and 80 ppm, between 2 and 70 ppm, between 2 and 60 ppm, between 2 and 50 ppm, between 2 and 40 ppm, between 2 and 30 ppm, between 2 and 20 ppm, between 2 and 15 ppm, between 2 and 10 ppm, between 3 and 90 ppm, between 3 and 80 ppm, between 3 and 70 ppm, between 3 and 60 ppm, between 3 and 50 ppm, between 3 and 40 ppm, between 3 and 30 ppm, between 3 and 20 ppm, between 3 and 15 ppm, between 3 and 10 ppm , between 4 and 100 ppm, between 4 and 90 ppm, between 4 and 80 ppm, between 4 and 70 ppm, between 4 and 60 ppm, between 4 and 50 ppm, between 4 and 40 ppm, between 4 and 30 ppm, between 4 and 20 ppm, between 4 and 15 ppm, between 4 and 10 ppm, between 5 and 100 ppm, between 5 and 90 ppm, between 5 and 80 ppm, between 5 and 70 ppm, between 5 and 60 ppm, between 5 and 50 ppm, between 5 and 40 ppm, between 5 and 30 ppm, between 5 and 20 ppm, between 5 and 15 ppm, or between 5 and 10 ppm by mass relative to the total mass the said salt.
    Advantageously, the method according to the invention leads to a LiFSI salt comprising a mass content of Cl 'less than or equal to 50 ppm, preferably less than or equal to 40 ppm, in particular less than or equal to 30 ppm, in particular less than or equal to 25 ppm by mass relative to the total mass of said salt.
    The process of the invention advantageously makes it possible to obtain a LiFSI whose mass contents of other impurities are as follows: F '<200 ppm, FSO3L1'<200 ppm, FSO2NH2 <200 ppm, CO3 2 '<50 ppm, CIO3'<50 ppm , CIO4 '<50ppm, NO2'<50ppm, NO3 '^ 50ppm, Si <40ppm, Mg <10ppm, Fe <10ppm, Ca <10ppm, Pb <10ppm, Cu <10ppm, Cr <10ppm, Ni <10ppm, Al < 10ppm, Zn <10ppm, and Na <10ppm.
    According to one embodiment, the method according to the invention advantageously leads to a LiFSI salt comprising:
    a mass content of water less than or equal to 45 ppm, preferably less than or equal to 40 ppm, preferably between 5 and 40 ppm, preferably between 8 and 40 ppm, in particular between 10 and 40 ppm, preferably between 12 and 40 ppm, for example between 15 and 40 ppm, in particular between 20 and 40 ppm, and advantageously between 25 and 40 ppm, and even more advantageously between 30 and 40 ppm;
    - a mass content of sulfate ions less than or equal to 100 ppm, less than or equal to 90 ppm, less than or equal to 80 ppm, less than or equal to 70 ppm, less than or equal to 60 ppm, less than or equal to 50 ppm, less or equal to 40 ppm, or less than or equal to 30 ppm, less than or equal to 20 ppm, less than or equal to 15 ppm, or less than or equal to 10 ppm by mass relative to the total mass of said salt; and
    - A mass Cl 'content less than or equal to 50 ppm, preferably less than or equal to 40 ppm, in particular less than or equal to 30 ppm, in particular less than or equal to 25 ppm by mass relative to the total mass of said salt.
    The present invention also relates to a LiFSI salt capable of being obtained according to the purification and drying process as described above, and to its uses in electrolytes from Li-ion batteries.
    The invention also relates to a process for the production of a lithium salt of bis (fluorosulfonyl) imide which comprises, in addition to steps i) to iv) mentioned above, steps a) to d) of the drying and purification process according to the invention.
    According to a second aspect, the invention relates to a process for the preparation of a lithium salt of bis (fluorosulfonyl) imide which comprises, upstream of steps a) to d) of the above-mentioned drying and purification process, steps i) to iv) following:
    i) synthesis of bis (chlorosulfonyl) imide;
    ii) fluorination of bis (chlorosulfonyl) imide to bis (fluorosulfonyl) imide;
    iii) preparation of the alkali or alkaline earth salt of bis (fluorosulfonyl) imide by neutralization of the bis (fluorosulfonyl) imide;
    iv) cation exchange to obtain a lithium salt of bis (fluorosulfonyl) imide.
    According to one embodiment, the lithium salt of bis (fluorosulfonyl) imide is prepared as described below.
    According to one embodiment, the present invention relates to a process for the preparation of a lithium salt of bis (fluorosulfonyl) imide comprising the following steps:
    i) synthesis of bis (chlorosulfonyl) imide from sulfamic acid;
    ii) fluorination of bis (chlorosulfonyl) imide to bis (fluorosulfonyl) imide;
    iii) preparation of the alkaline or alkaline-earth salt of bis (fluorosulfonyl) imide by neutralization of bis (fluorosulfonyl) imide, in particular using an aqueous solution of a base chosen from carbonates of alkali or alkaline metals earthy, and alkali or alkaline earth metal hydroxides;
    iv) cation exchange to obtain a lithium salt of bis (fluorosulfonyl) imide;
    v) drying and purification process according to the aforementioned invention, comprising steps a) to d) as described above.
    Step i): Synthesis of bischlorosulfonylimide
    Compound (A) containing two chlorosulfonyl groups (bis (chlorosulfonyl) imide), can be prepared from sulfamic acid, in particular according to the following scheme:
    OH
    Reagents
    H 2 N — S = O
    P / T
    CI (A)
    According to one embodiment, the reaction temperature is between 30 ° C and 150 ° C.
    According to one embodiment, the reaction time is between 1 hour and 7 days.
    According to one embodiment, the reaction can be carried out at a pressure between 1 bar absolute and 7 bar absolute.
    According to one embodiment, the “reactants” can be chlorosulfonic acid (CISO3H), and a chlorinating agent chosen from thionyl chloride (SOCb), oxalyl chloride (COCI) 2, phosphorus pentachloride (PCb ), phosphonyl trichloride (PCb), phosphoryl trichloride (POCI3) and their mixtures.
    According to the invention, a catalyst chosen from a tertiary amine such as methylamine, triethylamine, diethylmethylamine; pyridine; and 2,6-lutidine, can be added to accelerate the reaction.
    According to one embodiment, the molar ratio between chlorosulfonic acid and sulfamic acid is between 1 and 5.
    According to one embodiment, the molar ratio between the chlorinating agent and the sulfamic acid is between 2 and 5.
    According to another embodiment, the "reactants" can be sulfamic acid, and sulfuric acid or oleum, and a chlorinating agent chosen from thionyl chloride (SOCb), oxalyl chloride (COCI) 2, phosphorus pentachloride (PCb), phosphonyl trichloride (PCb), phosphoryl trichloride (POCb) and their mixtures. A catalyst chosen from a tertiary amine such as methylamine, triethylamine, diethylmethylamine, pyridine and 2,6-lutidine, can be added to accelerate the reaction. According to one embodiment, the molar ratio between sulfuric acid (or oleum) and sulfamic acid is between 0.7 and 5. According to one embodiment, the molar ratio between the chlorinating agent and the sulfamic acid is between 3 and 10.
    Step ii): Fluorination of bis (chlorosulfonyl) imide to bis (fluorosulfonyl) imide
    The process for preparing the LiFSI salt may comprise at least one step of reacting a compound of formula (A), in particular obtained at the end of step i) above, with anhydrous hydrofluoric acid, in at least minus an organic solvent.
    Step ii) allows in particular the fluorination of compound (A) into a compound (B) as described below.
    The fluorination step with anhydrous hydrofluoric acid, according to the present invention, can be diagrammed as follows:
    xHF / Solvents
    O o (A)
    P / T
    r \ // x o OO (B)
    Preferably, the solvent used in step ii) above is an organic solvent, in particular having a donor number between 1 and 70 advantageously between 5 and 65. The donor index of a solvent represents the value -ΔΗ, ΔΗ being the enthalpy of the interaction between the solvent and antimony pentachloride (Journal of Solution Chemistry, vol. 13, No. 9, 1984). As organic solvent, there may be mentioned in particular esters, nitriles or dinitriles, ethers or diethers, amines or phosphines. Combinations of these can also be used as the organic solvent.
    Methyl acetate, ethyl acetate, butyl acetate, acetonitrile, propionitrile, isobutyronitrile, glutaronitrile, dioxane, tetrahydrofuran, triethylamine, tripropylamine, diethylisopropylamine, pyridine , trimethylphosphine, triethylphosphine, diethylisopropylphosphine, and mixtures thereof, may be suitable as solvents.
    Preferably, the solvent is a polar aprotic organic solvent.
    Preferably, the organic solvent is dioxane.
    The reaction step with anhydrous hydrofluoric acid can be carried out at a temperature T, preferably between 0 ° C. and the boiling point of the solvent or of the mixture of solvents used. Advantageously, this temperature is between 5 ° C. and the boiling point of the solvent or of the mixture of solvents.
    The reaction step with anhydrous hydrofluoric acid can be carried out at a pressure P, preferably between 0 and 16 bar absolute.
    This step is preferably carried out by dissolving the compound of formula (A) in the solvent, or the mixture of solvents, prior to the reaction step with anhydrous HF.
    The mass ratio between the compound of formula (A) and the solvent, or the mixture of solvents, is preferably between 0.001 and 10, and advantageously between 0.005 and 5.
    According to one embodiment, the HF is introduced into the reaction medium, preferably in gaseous form.
    The molar ratio x between the HF and the compound of formula (A) used is preferably between 2 and 10, and advantageously between 2 and 5.
    The reaction step with HF can be carried out in a closed environment or in an open environment, preferably step iii) is carried out in an open environment with release of HCl in gas form.
    The use of a donor solvent makes it possible in particular to form a solvent-HF complex, and thus to enhance the nucleophilia of the fluorine atom. The use of such a complex advantageously allows gentle fluorination of the compound of formula (A), thus avoiding parasitic cleavage reactions.
    Step iii): Preparation of the bis (fluorosulfonyl) imide salt by neutralization of the bis (fluorosulfonyl) imide
    According to one embodiment, the process for preparing the lithium salt of bis (fluorosulfonyl) imide comprises, at the end of step ii) of fluorination, a neutralization step (step iii).
    According to one embodiment, the neutralization step is carried out using an aqueous solution of a base chosen from alkali or alkaline earth carbonate of formula MCC> 3, nH2O or alkali or alkali metal hydroxides -terrous MOH, nH2O, with M representing a monovalent cation of alkali or alkaline-earth metal. Preferably, MOH represents NaOH, KOH RbOH, and CsOH. Preferably, MCO3 represents Na 2 CO3, K2CO3, Rb 2 CO3, CS2CO3.
    Preferably, M does not represent Li.
    Preferably, the base used is not a base comprising lithium. Preferably, the base used comprises potassium.
    The above step iii) is carried out in particular according to the following diagram:
    O F
    W / NH / SC S
    W //
    O o
    Based
    O \
    F X W // OO (C)
    Preferably, the neutralization step leads to a solution of (C) having a pH greater than 4.
    In particular, the residual HF and / or the residual HCI dissolved in the solvent reacts with the base described above, so as to form an alkali or alkaline earth metal fluoride MF (or a mixture of MF fluorides), respectively an alkali or alkaline earth metal chloride MCI (or a mixture of chlorides MCI). The neutralization reaction can be carried out for example by adding an aqueous solution of the chosen base. The base / compound molar ratio (B) can be, for example, from 1 to 5 when the base is a hydroxide, or from 0.5 to 5 (or from 2 to 10), when the base is a carbonate. The reaction temperature can, for example, be between −10 ° C. and 40 ° C.
    According to the invention, the aqueous solution comprising the compound (C) can then be filtered.
    Depending on the nature of the alkali or alkaline earth metal, the product (C) may be present in the filtrate or in the filtered solid. The alkali or alkaline earth metal fluorides are present in particular in the filtered solid but can also be found in the filtrate.
    Two different product recovery steps (C) can be used at the end of step iii), depending on where the product (C) is mainly located: step R1 or step R2.
    According to a first recovery mode (step R1), when the product (C) is mainly contained in the aqueous phase (filtrate), the aqueous phase can be extracted with an organic solvent chosen from the following families: esters, nitriles , ethers, chlorinated solvents, aromatic solvents, and mixtures thereof. Preferably, the organic solvent is chosen from dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran, acetronitrile, diethyl ether, and their mixtures. In particular, it is butyl acetate.
    For each extraction, the mass quantity of organic solvent used can vary between 1/6 and 1 times the mass of the aqueous phase. The number of extractions can be between 2 and 10. Preferably, the organic phase, resulting from the extraction, has a mass content of bis (fluorosulfonyl) imide salt ranging from 5 to 50% by mass. The organic phase can then be concentrated to reach a bis (fluorosulfonyl) imide salt concentration of between 5 and 55%, preferably between 10% and 50% by mass, said concentration can be achieved by any known means of evaporation of the skilled person.
    According to a second recovery mode (step R2), when it is mainly contained in the cake (filtered solid), the product (C) can be recovered by washing the cake with an organic solvent chosen from the following families: esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and mixtures thereof. Preferably, the organic solvent is chosen from dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran, acetronitrile, diethyl ether, and their mixtures. In particular, it is butyl acetate.
    The mass amount of organic solvent used can vary between 1 and 10 times the weight of the cake. The total amount of organic solvent intended for washing can be used at once or in several times with the aim in particular of optimizing the dissolution of the product (C). Preferably, the organic phase, resulting from the extraction, has a mass content of LiFSI salt ranging from 5 to 50% by mass. The organic phase can then be concentrated to reach a bis (fluorosulfonyl) imide salt concentration of between 5 and 55%, preferably between 10% and 50% by mass, said concentration can be achieved by any known means of evaporation of the skilled person.
    Preferably, the compound (C) is such that M = K.
    Step iv: cation exchange to obtain a lithium salt of bis (fluorosulfonyl) imide
    A final cation exchange step can be carried out, for example according to the following diagram:
    O \ / NM W /
    F ^ \ //
    O o
    O O (C)
    -MX where M 1 = Li and X can be a fluoride, a chloride, a carbonate, a hydroxide, a sulfate, a chlorate, a perchlorate, a nitrite or a nitrate.
    The salt M 1 X can be dissolved in a polar organic solvent chosen from the following families: alcohols, nitriles and carbonates. By way of example, mention may in particular be made of methanol, ethanol, acetonitrile, dimethylcarbonate and ethylmethylcarbonate.
    This solution can be poured into a solution of the product (C) in an organic solvent chosen from the following families: esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and mixtures thereof. Preferably, the solvent is chosen from dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran, acetronitrile, diethyl ether, and their mixtures. Preferably, the solvent is butyl acetate.
    The molar ratio of the product (C) relative to M 1 X can vary: it can be at least 1 and less than 5. Preferably the molar ratio (C) / M 1 X is between 1.2 and 2 .
    The reaction medium can be left under stirring for 1 to 24 hours at a temperature of, for example, between 0 and 50 ° C. At the end of the reaction, the reaction medium can be filtered to remove the MX precipitate formed. The filtrate can then be concentrated to remove the solvent from the salt M 1 X with a boiling point less than or equal to 90 ° C. An MX precipitate can then form again and be removed by filtration. Thanks to this purification, the relative mass ratio of the impurity M with respect to the product (D) is advantageously less than or equal to 500 ppm.
    According to a first embodiment, the solution of the product (D) obtained after the filtration (s) is evaporated, either by a thin film evaporator, or by an atomizer, or by a rotary evaporator, or by all other device allowing solvent evaporation.
    Compound (D) can then be subjected to the purification process according to the invention described above, comprising in particular the following steps:
    a) addition of deionized water to dissolve and extract the lithium salt of bis (fluorosulfonyl) imide, forming an aqueous solution of said salt;
    a ’) possible concentration of said aqueous solution of said salt;
    b) extraction of the lithium salt of bis (fluorosulfonyl) imide from said aqueous solution, with an organic solvent S2, preferably said solvent S2 forming an azeotropic mixture with water, this step being repeated at least once;
    c) concentration of the lithium salt of bis (fluorosulfonyl) imide by evaporation of said organic solvent S2 and of water, in a short-film thin film evaporator, under the following conditions:
    - temperature between 30 ° C and 95 ° C, preferably between 30 ° C and
    90 ° C, preferably between 40 ° C and 85 ° C;
    - pressure between 10 ' 3 mbar abs and 5 mbar abs;
    - residence time less than or equal to 15 min, preferably less than or equal to 10 minutes preferably less than or equal to 5 minutes;
    d) optionally crystallization of the lithium salt of the bis (fluorosulfonyl) imide.
    The product (D) purified according to the process of the invention, is advantageously in the form of a white powder.
    The present invention also relates to a lithium salt of bis (fluorosulfonyl) imide comprising:
    a mass content of water of between 5 and 45 ppm, preferably between 5 and 40 ppm by mass relative to the total mass of said salt; and a mass content of sulfate ions less than or equal to 100 ppm, preferably less than or equal to 90 ppm, less than or equal to 80 ppm, less than or equal to 70 ppm, less than or equal to 60 ppm, less than or equal to 50 ppm , less than or equal to 40 ppm, or less than or equal to 30 ppm, less than or equal to 20 ppm, less than or equal to 15 ppm, or less than or equal to 10 ppm by mass relative to the total mass of said salt.
    In the LiFSI salt according to the invention, the mass proportion of water can be for example between 8 and 45 ppm, between 9 and 45 ppm, between 10 and 45 ppm, between 11 and 45 ppm, between 12 and 45 ppm, between 13 and 45 ppm, between 14 and 45 ppm, between 15 and 45 ppm, between 16 and 45 ppm, between 17 and 45 ppm, between 18 and 45 ppm, between 19 and 45 ppm, between 20 and 45 ppm, between 21 and 45 ppm, between 22 and 45 ppm, between 23 and 45 ppm, between 24 and 45 ppm, between 25 and 45 ppm, between 26 and 45 ppm, between 27 and 45 ppm, between 28 and 45 ppm, between 29 and 45 ppm , between 30 and 45 ppm, 8 and 40 ppm, between 9 and 40 ppm, between 10 and 40 ppm, between 11 and 40 ppm, between 12 and 40 ppm, between 13 and 40 ppm, between 14 and 40 ppm, between 15 and 40 ppm, between 16 and 40 ppm, between 17 and 40 ppm, between 18 and 40 ppm, between 19 and 40 ppm, between 20 and 40 ppm, between 21 and 40 ppm, between 22 and 40 ppm, between 23 and 40 ppm, between 24 and 40 ppm, between 25 and 40 ppm, between 26 and 40 ppm, between 27 and 40 ppm, between 28 and 40 ppm, between 29 and 40 ppm, or between 30 and 40 ppm by mass relative to the total mass of said salt.
    In the LiFSI salt according to the invention, the mass proportion of sulfate ions can for example be between 2 and 100 ppm, between 2 and 90 ppm, between 2 and 80 ppm, between 2 and 70 ppm, between 2 and 60 ppm, between 2 and 50 ppm, between 2 and 40 ppm, between 2 and 30 ppm, between 2 and 20 ppm, between 2 and 15 ppm, between 2 and 10 ppm, between 3 and 90 ppm, between 3 and 80 ppm, between 3 and 70 ppm, between 3 and 60 ppm, between 3 and 50 ppm, between 3 and 40 ppm, between 3 and 30 ppm, between 3 and 20 ppm, between 3 and 15 ppm, between 3 and 10 ppm, between 4 and 100 ppm , between 4 and 90 ppm, between 4 and 80 ppm, between 4 and 70 ppm, between 4 and 60 ppm, between 4 and 50 ppm, between 4 and 40 ppm, between 4 and 30 ppm, between 4 and 20 ppm, between 4 and 15 ppm, between 4 and 10 ppm, between 5 and 100 ppm, between 5 and 90 ppm, between 5 and 80 ppm, between 5 and 70 ppm, between 5 and 60 ppm, between 5 and 50 ppm, between 5 and 40 ppm, between 5 and 30 ppm, between 5 and 20 ppm, between 5 and 15 ppm, or between 5 and 10 ppm by mass relative to the total mass of said salt.
    According to one embodiment, the LiFSI salt comprises a content of Cf ions less than or equal to 50 ppm, preferably less than or equal to 40 ppm, in particular less than or equal to 30 ppm, in particular less than or equal to 25 ppm by mass relative to to the total mass of said salt.
    In particular, the LiFSI salt according to the invention comprises the following impurities: F '<200 ppm (preferably <50 ppm), FSChLi <200 ppm, FSO2NH2S 200 ppm, CO3 2 ' ^ 50 ppm, CIO3 's 50 ppm, CIO4 's 50 ppm, NO2' s 50 ppm, NO3 's 50 ppm, Si <40 ppm, Mg <10 ppm, Fe <10 ppm, Ca <10ppm, Pb <10ppm, Cu <10 ppm, Cr <10 ppm , Ni <10 ppm, Al <10 ppm, Zn <10 ppm, and Na <10 ppm.
    According to a preferred embodiment, the LiFSI according to the invention comprises:
    - a mass content of water between 5 and 45 ppm, and in particular between for example between 8 and 45 ppm, between 9 and 45 ppm, between 10 and 45 ppm, between 11 and 45 ppm, between 12 and 45 ppm, 13 and 45 ppm, between 14 and 45 ppm, between 15 and 45 ppm, between 16 and 45 ppm, between 17 and 45 ppm, between 18 and 45 ppm, between 19 and 45 ppm, between 20 and 45 ppm, between 21 and 45 ppm, between 22 and 45 ppm, between 23 and 45 ppm, between 24 and 45 ppm, between 25 and 45 ppm, between 26 and 45 ppm, between 27 and 45 ppm, between 28 and 45 ppm, between 29 and 45 ppm , between 30 and 45 ppm, or between 30 and 40 ppm by mass relative to the total mass of said salt;
    - a mass content of sulfate ions less than or equal to 100 ppm, for example between 2 and 100 ppm, between 2 and 90 ppm, between 2 and 80 ppm, between 2 and 70 ppm, between 2 and 60 ppm, between 2 and 50 ppm, between 2 and 40 ppm, between 2 and 30 ppm, between 2 and 20 ppm, between 2 and 15 ppm, between 2 and 10 ppm, between 3 and 90 ppm, between 3 and 80 ppm, between 3 and 70 ppm , between 3 and 60 ppm, between 3 and 50 ppm, between 3 and 40 ppm, between 3 and 30 ppm, between 3 and 20 ppm, between 3 and 15 ppm, between 3 and 10 ppm, between 4 and 100 ppm, between 4 and 90 ppm, between 4 and 80 ppm, between 4 and 70 ppm, between 4 and 60 ppm, between 4 and 50 ppm, between 4 and 40 ppm, between 4 and 30 ppm, between 4 and 20 ppm, between 4 and 15 ppm, between 4 and 10 ppm, between 5 and 100 ppm, between 5 and 90 ppm, between 5 and 80 ppm, between 5 and 70 ppm, between 5 and 60 ppm, between 5 and 50 ppm, between 5 and 40 ppm , between 5 and 30 ppm, between 5 and 20 ppm, between 5 and 15 ppm, or between 5 and 10 ppm by mass relative to the total mass of said salt;
    - And preferably a mass content of Cf less than or equal to 50 ppm, preferably less than or equal to 40 ppm, in particular less than or equal to 30 ppm, in particular less than or equal to 25 ppm by mass relative to the total mass of said salt .
    According to one embodiment, the LiFSI according to the invention is characterized in that the sum of the water content and the sulphate content is less than or equal to 100 ppm ([H2O] + [SO4 2 '] s 100 ppm ), preferably between 2 and 100 ppm, preferably between 5 and 100 ppm, in particular between 5 and 90 ppm, preferably between 5 and 90 ppm, for example between 10 and 90 ppm, and advantageously between 10 and 60 ppm.
    According to a preferred embodiment, the LiFSI according to the invention comprises:
    - a mass content of water between 5 and 45 ppm, and in particular between for example between 8 and 45 ppm, between 9 and 45 ppm, between 10 and 45 ppm, between 11 and 45 ppm, between 12 and 45 ppm, 13 and 45 ppm, between 14 and 45 ppm, between 15 and 45 ppm, between 16 and 45 ppm, between 17 and 45 ppm, between 18 and 45 ppm, between 19 and 45 ppm, between 20 and 45 ppm, between 21 and 45 ppm, between 22 and 45 ppm, between 23 and 45 ppm, between 24 and 45 ppm, between 25 and 45 ppm, between 26 and 45 ppm, between 27 and 45 ppm, between 28 and 45 ppm, between 29 and 45 ppm , between 30 and 45 ppm, or between 30 and 40 ppm by mass relative to the total mass of said salt;
    - a mass content of sulfate ions less than or equal to 100 ppm, for example between 2 and 100 ppm, between 2 and 90 ppm, between 2 and 80 ppm, between 2 and 70 ppm, between 2 and 60 ppm, between 2 and 50 ppm, between 2 and 40 ppm, between 2 and 30 ppm, between 2 and 20 ppm, between 2 and 15 ppm, between 2 and 10 ppm, between 3 and 90 ppm, between 3 and 80 ppm, between 3 and 70 ppm , between 3 and 60 ppm, between 3 and 50 ppm, between 3 and 40 ppm, between 3 and 30 ppm, between 3 and 20 ppm, between 3 and 15 ppm, between 3 and 10 ppm, between 4 and 100 ppm, between 4 and 90 ppm, between 4 and 80 ppm, between 4 and 70 ppm, between 4 and 60 ppm, between 4 and 50 ppm, between 4 and 40 ppm, between 4 and 30 ppm, between 4 and 20 ppm, between 4 and 15 ppm, between 4 and 10 ppm, between 5 and 100 ppm, between 5 and 90 ppm, between 5 and 80 ppm, between 5 and 70 ppm, between 5 and 60 ppm, between 5 and 50 ppm, between 5 and 40 ppm , between 5 and 30 ppm, between 5 and 20 ppm, between 5 and 15 ppm, or between 5 and 10 ppm by mass relative to the total mass of said salt;
    - a mass Cl 'content less than or equal to 50 ppm;
    - A mass content of F 'less than or equal to 200 ppm, preferably less than or equal to 50 ppm;
    - a mass content of FSO3L1 less than or equal to 200 ppm;
    - a mass content of FSO2NH2 less than or equal to 200 ppm;
    - a mass content of COs 2- less than or equal to 50 ppm;
    - a mass content of CIO3 'less than or equal to 50 ppm;
    - a mass content of CIO4 'less than or equal to 50 ppm;
    - a mass content of NO2 'less than or equal to 50 ppm;
    - a mass content of NO3 'less than or equal to 50 ppm;
    - a mass content of Si less than or equal to 40 ppm;
    - a mass content of Mg less than or equal to 10 ppm;
    - a mass content of Fe less than or equal to 10 ppm;
    - a mass content of Ca less than or equal to 10 ppm;
    - a mass content of Pb less than or equal to 10 ppm;
    - a mass content of Cu less than or equal to 10 ppm;
    - a mass content of Cr less than or equal to 10 ppm;
    - a mass content of Ni less than or equal to 10 ppm;
    - a mass content of Al less than or equal to 10 ppm;
    - a mass content of Zn less than or equal to 10 ppm; and
    - a mass content of Na less than or equal to 10 ppm.
    According to a preferred embodiment, the LiFSI according to the invention comprises:
    - A mass content of water between 5 and 45 ppm, and in particular between 10 and 40 ppm by mass relative to the total mass of said salt; and
    - A mass content of sulfate ions of between 3 and 40 ppm, preferably between 5 and 10 ppm by mass relative to the total mass of said salt.
    The present invention also relates to an electrolyte comprising the LiFSI salt according to the invention, namely comprising:
    a mass content of water of between 5 and 45 ppm, preferably between 5 and 40 ppm by mass relative to the total mass of said salt; and a mass content of sulfate ions less than or equal to 100 ppm, preferably less than or equal to 90 ppm, less than or equal to 80 ppm, less than or equal to 70 ppm, less than or equal to 60 ppm, less than or equal to 50 ppm , less than or equal to 40 ppm, or less than or equal to 30 ppm, less than or equal to 20 ppm, less than or equal to 15 ppm, or less than or equal to 10 ppm by mass relative to the total mass of said salt.
    The present invention also relates to the use of the LiFSI salt according to the invention in Li-ion batteries, in particular in electrolytes of Li-ion batteries.
    In particular, the LiFSI salt according to the invention can be used in Liion batteries of portable devices (for example mobile phones, cameras, tablets or portable computers), or of electric vehicles, or of energy storage. renewable (such as photovoltaic or wind).
    The LiFSI salt can in particular be used in “pocket” type batteries (also known under the term “Pouch Cell”).
    The LiFSI salt can advantageously be used for high or low temperature applications.
    The LiFSI salt according to the invention advantageously has at least one of the following advantages:
    reduced risk of short circuit, ignition or battery explosion;
    longer service life;
    increased number of charge cycles;
    reduction or even elimination of corrosion of the battery components, such as the AI collector;
    reduction of the risks of swelling of the battery, in particular of flexible “pocket” type batteries (known under the term “Pouch cell”); good resistance to high and / or low temperature.
    In the context of the invention, by "lying between x and y", or "ranging from x to y", is meant an interval in which the limits x and y are included. For example, the temperature "between 30 and 100 ° C." includes in particular the values 30 ° C. and 100 ° C.
    All of the embodiments described above can be combined with each other. In particular, each embodiment of any step of the process of the invention can be combined with another particular embodiment. Likewise, each content of the constituents of the LiFSI salt can be combined with each other.
    The present invention is illustrated by the following example, to which it is not however limited.
    Example 1: Purification and concentration of a LiFSI solution
    Different impurities present in the lithium salt of bis (fluorosulfonyl) imide were analyzed and the results obtained are presented below.
    Purification of a LiFSI solution in butyl acetate.
    Or a solution containing 166g of LiFSI (which can for example be obtained according to the method described in WO2015158979) in 830 g of butyl acetate. It is concentrated in a rotary evaporator heated to 40 ° C under vacuum (pressure <30mbar). A solution is obtained whose dry extract is 37% by mass. An aqueous extraction of the LiFSI contained is carried out, in 3 times (1/2 mass of water relative to the mass of the concentrated solution (dry extract of 37% by mass), then 1/3 mass of water relative to the mass of the concentrated solution (dry extract of 37% by mass), then 1/4 of mass of water relative to the mass of the concentrated solution (dry extract of 37% by mass)). The aqueous phases are combined (aqueous solution having a dry extract of 21%) which is concentrated by evaporation under vacuum (P <30mbar) at 40 ° C, to lead to an aqueous solution whose dry extract is 35% . The recovery yield of LiFSI is 77%. The LiFSI dissolved in water is then re-extracted by 4 successive extractions in butyl acetate by 1/4 of the mass of the aqueous solution. A solution of LiFSI in butyl acetate is obtained (dry extract of approximately 13%). The extraction yield is 65% in LiFSI. The solvent phase extractions are combined, which are first concentrated by a rotary evaporator at 40 ° C. under reduced pressure (P <30mbar).
    Concentration of a LiFSI solution to obtain solid LiFSI
    The last concentration is carried out on a WFSP (Wipped Film Short Path) film evaporation apparatus at a temperature of 80 ° C. under a vacuum of 0.5 mbar, for a residence time of approximately 2 minutes.
    The concentrate is taken up in dichloromethane. LiFSI crystallizes quickly. 89g of LiFSI are obtained which are recovered by filtration and which are placed under vacuum for at least 24 hours. The analysis is given below.
    Sampling for quantification of Li, Na and traces of elements from the list provided:
    The sample of the lithium salt of bis (fluorosulfonyl) imide obtained according to the method described above is dissolved in ultrapure water. Two dilutions were used: 1 g / l for the determination of Na, and elements Ag, Al, As, Ba, Si, Cd, Co, Cr, Cu, Ni, Pb, Sb, Se, Sn, Sr, Ti, Zn at trace level, and 0.1 g / l for the analysis of Lithium.
    Panoramic qualitative analysis:
    The ICP-AES conditions (inductively coupled plasma spectrometry) applied for the semi-quantitative so-called panoramic analysis of trace elements are:
    Plasma source output power: 1150 W;
    Nebulization gas flow: 0.7 L / min;
    Cooling flow = 16 L / min;
    Torch height: 12 mm;
    - Pump speed: 50 rpm;
    Spectral bandwidth: 7 pm at 200 nm, 3.5 nm per pixel;
    Wavelength range: 167 nm to 847 nm.
    The ICP-AES method of quantification to measure Li, Na used 5 calibration points. ICP-AES data is obtained on an ICAP 6500 spectrometer (Thermo Electronics).
    For the analysis of trace elements Ag, Al, As, Ba, Si, Cd, Co, Cr, Cu, Ni, Pb, Sb, Se, Sn, Sr, Ti, Zn, the semi-method quantitative is based on two calibration points.
    For both methods, calibration is performed by adding standards to the sample itself so as to minimize matrix effects.
    ICP-AES is preferred to cationic chromatography in aqueous solution for the measurement of Li, Na elements.
    The conditions for analyzing anions in ion chromatography (Cl) are as follows:
    - Thermo ICS 5000 DUAL device;
    AS16-HC column;
    Flow rate 1 ml / min;
    Eluent KOH isocratic at 20 mmol / l;
    Conductimetric detection;
    ASRS suppressor 4 mm with 50 mA of imposed current;
    Injection of 25 μl of LiFSI solutions at 5 g / l and 10 g / I according to the sensitivity required by anionic species present;
    Calibration of each anionic species with five synthetic solutions ranging from 0.1 mg / l up to 25 mg / l.
    The NMR analysis conditions of the fluorinated species such as FSO3L1 and FSO2NH2 in 19 F, H1 NMR are as follows:
    Equipment: The NMR spectra and quantifications were carried out on a Bruker AV 400 spectrometer, at 1376.47 MHz for 19 F, on a 5 mm probe of the BBFO + type. Sampling:
    The samples are dissolved in DMSO-d6 (approximately 30 mg in 0.6 ml). In the case of the detection of fluorides or the addition of Li F used to verify the undesirable presence of fluorides, the solvent used is D2O due to the insolubility of LiF in DMSO. Quantification:
    The relative quantification in NMR of fluorine 19 (NMR 19 F) is made by integration of the signals of the fluorinated species, weighted by the number of fluorine contributing to the signal, a method well known to those skilled in the art.
    The absolute quantification in 19 F NMR is made by metered addition of a, a, a-trifluorotoluene (TFT), Aldrich in the tube containing the sample, and by integration of the signals of the fluorinated species to be assayed in comparison with that of the CF 3 of this internal standard, according to a method well known to those skilled in the art. The limit of quantification of a species is of the order of fifty ppm.
    Water content :
    Carried out by dosing of the Karl Fischer 684 KF coulometer type coupled with the 860 KF Thermoprep (Metrohm equipment).
    The solid LiFSI sample is transferred to a glove box in a bottle suitable for 10 Thermoprep. It is heated for 30 minutes at 50 ° C. then the gas phase is introduced into the metering cell of the KF titrimeter.
    The results obtained are presented in Table I.
    Species Quantity Method of analysis FSO2NH2 ND RMN 19 F FSO 3 Li ND RMN 19 F H 2 O 40 ppm Karl Fischer SO 4 2 - 7 ppm Cl cr 22 ppm Cl F- ND NMR co 3 2 - ND Cl IOC ND Cl CIO4 ND Cl no 2 - ND Cl no 3 - ND Cl Mg ND ICP Yes ND FX Fe ND ICP It ND ICP Pb ND ICP Cu ND ICP Cr ND ICP Or ND ICP Al ND ICP Zn ND ICP N / A ND ICP
    ND: not detected
    Table I
    The process according to the invention advantageously makes it possible to obtain a LiFSI salt having a reduced content of both water and sulfate ions.
    权利要求:
    Claims (18)
    [1" id="c-fr-0001]
    1. Method for drying and purifying a lithium salt of bis (fluorosulfonyl) imide in solution in an organic solvent S1, said method comprising the following steps:
    a) addition of deionized water to dissolve and extract the lithium salt of bis (fluorosulfonyl) imide, forming an aqueous solution of said salt;
    a ’) possible concentration of said aqueous solution of said salt;
    b) extraction of the lithium salt of bis (fluorosulfonyl) imide from said aqueous solution, with an organic solvent S2, this step being repeated at least once;
    c) concentration of the lithium salt of bis (fluorosulfonyl) imide by evaporation of said organic solvent S2 and of water, in a short-film thin film evaporator, under the following conditions:
    - temperature between 30 ° C and 95 ° C, preferably between 30 ° C and 90 ° C, preferably between 40 ° C and 85 ° C;
    - pressure between 10 ' 3 mbar abs and 5 mbar abs;
    - residence time less than or equal to 15 min, preferably less than or equal to 10 min;
    d) optionally crystallization of the lithium salt of bis (fluorosulfonyl) imide.
    [2" id="c-fr-0002]
    2. Method according to claim 1, comprising step a ') of concentration of said aqueous solution, preferably to obtain an aqueous solution comprising a content of lithium salt of bis (fluorosulfonyl) imide of between 20% and 80%, preferably between 30% and 65%.
    [3" id="c-fr-0003]
    3. The method of claim 1 or claim 2, wherein the organic solvent S2 is selected from the group consisting of organic carbonates, ethers, esters and their mixtures.
    [4" id="c-fr-0004]
    4. The method of claim 3, wherein the organic solvent S2 is selected from the group consisting of methyl-t-butyl ether, cyclopentylmethyl ether, ethyl acetates, propyl and butyl, and mixtures thereof, preferably the organic solvent S2 is butyl acetate.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1 to 4, in which the mass ratio organic solvent S2 / water, during an extraction, varies from 1/6 to 1/1, and the number of extracts varying in particular from 2 to 10.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 5, wherein step c) of concentration is carried out at a pressure between 10 ' 2 mbar abs and 5 mbar abs, preferably between 5.10' 2 mbar abs and 2 mbar abs, preferably between 0.1 and 1 mbar abs, and in particular between 0.4 and 0.6 mbar abs.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 6, wherein step c) is carried out at a temperature between 30 ° C and 95 ° C, preferably between 30 ° C and 90 ° C, preferably between 40 ° C and 85 ° C, and in particular between 60 ° C and 80 ° C, advantageously at 80 ° C.
    [8" id="c-fr-0008]
    8. Method according to any one of claims 1 to 7, in which step c) is carried out with a residence time less than or equal to 5 min, in particular less than or equal to 3 min.
    [9" id="c-fr-0009]
    9. Method according to any one of claims 1 to 8, in which, during step d), the lithium salt of bis (fluorosulfonyl) imide is cold crystallized at a temperature less than or equal to 25 ° C, optionally in an organic solvent S3 chosen from chlorinated solvents, such as for example dichloromethane, and aromatic solvents, such as for example toluene, said salt being optionally recovered by filtration.
    [10" id="c-fr-0010]
    10. Method according to any one of claims 1 to 9, characterized in that it leads to a lithium salt of bis (fluorosulfonyl) imide comprising water with a content less than or equal to 45 ppm relative to the total mass of said salt, and preferably sulfate ions at a content less than or equal to 100 ppm.
    [11" id="c-fr-0011]
    11. A lithium salt of bis (fluorosulfonyl) imide capable of being obtained according to the process of any one of claims 1 to 10.
    [12" id="c-fr-0012]
    12. Process for the production of a bis (fluorosulfonyl) imide lithium salt comprising the following steps:
    i. synthesis of bis (chlorosulfonyl) imide from sulfamic acid;
    ii. fluorination of bis (chlorosulfonyl) imide to bis (fluorosulfonyl) imide, and iii. preparation of the alkali or alkaline earth salt of bis (fluorosulfonyl) imide by neutralization of the bis (fluorosulfonyl) imide, in particular using an aqueous solution of a base chosen from carbonates of alkali or alkaline earth metals, and alkali or alkaline earth metal hydroxides, iv. cation exchange to obtain a lithium salt of bis (fluorosulfonyl) imide; and
    v. drying and purification process according to any one of claims 1 to 10.
    [13" id="c-fr-0013]
    13. Bis (fluorosulfonyl) imide lithium salt comprising:
    a mass content of water of between 5 and 45 ppm, preferably between 5 and 40 ppm by mass relative to the total mass of said salt; and
    - a mass content of sulfate ions less than or equal to 100 ppm, preferably less than or equal to 90 ppm, less than or equal to 80 ppm, less than or equal to 70 ppm, less than or equal to 60 ppm, less than or equal to 50 ppm , less than or equal to 40 ppm, or less than or equal to 30 ppm, less than or equal to 20 ppm, less than or equal to 15 ppm, or less than or equal to 10 ppm by mass relative to the total mass of said salt.
    [14" id="c-fr-0014]
    14. A lithium salt of bis (fluorosulfonyl) imide according to claim 13, comprising a mass content of sulfate ions between 2 and 100 ppm, between 2 and 90 ppm, between 2 and 80 ppm, between 2 and 70 ppm, between 2 and 60 ppm, between 2 and 50 ppm, between 2 and 40 ppm, between 2 and 30 ppm, between 2 and 20 ppm, between 2 and 15 ppm, between 2 and 10 ppm, between 3 and 90 ppm, between
    3 and 80 ppm, between 3 and 70 ppm, between 3 and 60 ppm, between 3 and 50 ppm, between 3 and 40 ppm, between 3 and 30 ppm, between 3 and 20 ppm, between 3 and 15 ppm, between 3 and 10 ppm, between 4 and 100 ppm, between 4 and 90 ppm, between 4 and 80 ppm, between 4 and 70 ppm, between 4 and 60 ppm, between 4 and 50 ppm, between 4 and 40 ppm, between 4 and 30 ppm , between 4 and 20 ppm, between 4 and 15 ppm, between
    4 and 10 ppm, between 5 and 100 ppm, between 5 and 90 ppm, between 5 and 80 ppm, between 5 and 70 ppm, between 5 and 60 ppm, between 5 and 50 ppm, between 5 and 40 ppm, between 5 and 30 ppm, between 5 and 20 ppm, between 5 and 15 ppm, or between 5 and 10 ppm by mass relative to the total mass of said salt.
    [15" id="c-fr-0015]
    15. A lithium salt of bis (fluorosulfonyl) imide according to any one of claims 13 or 14, comprising:
    - a mass content of water between 5 and 45 ppm, and in particular between for example between 8 and 45 ppm, between 9 and 45 ppm, between 10 and 45 ppm, between 11 and 45 ppm, between 12 and 45 ppm, 13 and 45 ppm, between 14 and 45 ppm, between 15 and 45 ppm, between 16 and 45 ppm, between 17 and 45 ppm, between 18 and 45 ppm, between 19 and 45 ppm, between 20 and 45 ppm, between 21 and 45 ppm, between 22 and 45 ppm, between 23 and 45 ppm, between 24 and 45 ppm, between 25 and 45 ppm, between 26 and 45 ppm, between 27 and 45 ppm, between 28 and 45 ppm, between 29 and 45 ppm , between 30 and 45 ppm, or between 30 and 40 ppm by mass relative to the total mass of said salt;
    - a mass content of sulfate ions less than or equal to 100 ppm, for example between 2 and 100 ppm, between 2 and 90 ppm, between 2 and 80 ppm, between 2 and 70 ppm, between 2 and 60 ppm, between 2 and 50 ppm, between 2 and 40 ppm, between 2 and 30 ppm, between 2 and 20 ppm, between 2 and 15 ppm, between 2 and 10 ppm, between 3 and 90 ppm, between 3 and 80 ppm, between 3 and 70 ppm , between 3 and 60 ppm, between 3 and 50 ppm, between 3 and 40 ppm, between 3 and 30 ppm, between 3 and 20 ppm, between 3 and 15 ppm, between 3 and 10 ppm, between 4 and 100 ppm, between 4 and 90 ppm, between 4 and 80 ppm, between 4 and 70 ppm, between 4 and 60 ppm, between 4 and 50 ppm, between 4 and 40 ppm, between 4 and 30 ppm, between 4 and 20 ppm, between 4 and 15 ppm, between 4 and 10 ppm, between 5 and 100 ppm, between 5 and 90 ppm, between 5 and 80 ppm, between 5 and 70 ppm, between 5 and 60 ppm, between 5 and 50 ppm, between 5 and 40 ppm , between 5 and 30 ppm, between 5 and 20 ppm, between 5 and 15 ppm, or between 5 and 10 ppm by mass relative to the total mass of said salt;
    a mass content of Cl less than or equal to 50 ppm, preferably less than or equal to 40 ppm, in particular less than or equal to 30 ppm, in particular less than or equal to 25 ppm by mass relative to the total mass of said salt.
    [16" id="c-fr-0016]
    16. Bis (fluorosulfonyl) imide lithium salt according to any one of claims 13 to 15, characterized in that the sum of the water content and the sulphate content is less than or equal to 100 ppm, preferably included between 2 and 100 ppm, preferably between 5 and 100 ppm, in particular between 5 and 90 ppm, preferably between 5 and 90 ppm, for example between 10 and 90 ppm, and advantageously between 10 and 60 ppm.
    [17" id="c-fr-0017]
    17. Use of a bis (fluorosulfonyl) imide lithium salt according to one
    5 any of claims 13 to 16 in Li-ion batteries.
    [18" id="c-fr-0018]
    18. Use according to claim 17, in portable devices, for example mobile phones, cameras, tablets or portable computers, in electric vehicles, or in storage
    10 of renewable energy (such as photovoltaic or wind).
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1662130A|FR3059994B1|2016-12-08|2016-12-08|LIFSI DRYING AND PURIFICATION PROCESS|
    FR1662130|2016-12-08|FR1662130A| FR3059994B1|2016-12-08|2016-12-08|LIFSI DRYING AND PURIFICATION PROCESS|
    CN201780068664.3A| CN109982966A|2016-12-08|2017-12-07|Dry and purifying LiFSI method|
    PCT/FR2017/053447| WO2018104675A1|2016-12-08|2017-12-07|Method for drying and purifying lifsi|
    JP2019515208A| JP6917447B2|2016-12-08|2017-12-07|Methods for drying and purifying LiFSI|
    KR1020197009225A| KR102337612B1|2016-12-08|2017-12-07|LIFSI drying and purification method|
    US16/331,242| US11084723B2|2016-12-08|2017-12-07|Method for drying and purifying LiFSI|
    EP17816998.3A| EP3494086A1|2016-12-08|2017-12-07|Method for drying and purifying lifsi|
    US17/358,819| US20210323823A1|2016-12-08|2021-06-25|METHOD FOR DRYING AND PURIFYING LiFSI|
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