Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
  • C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
  • C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
  • C01B21/092—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more metal atoms
  • C01B21/0923—Metal imides or amides
  • C01B21/0926—Metal imides or amides of alkali metals
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
  • C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
  • C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
  • C01B21/0935—Imidodisulfonic acid; Nitrilotrisulfonic acid; Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
  • C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a process for preparing ammonium salts containing a fluorosulfonyl group.
• the present invention also relates to a process for preparing lithium salts of imides containing a fluorosulfonyl group.
• Sulfonylimide type anions due to 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 supercapacitors or in the field of liquids. ionic. With the battery market booming and the reduction of battery manufacturing costs becoming a major issue, a large-scale, low-cost synthesis process for this type of anions is needed.
• LiPF 6 LiPF 6
• LiPF 6 LiPF 6
• LiFSI LiN (FS0 2 ) 2
• LiFSI LiFSI
• the examples of EP2505551 describe in particular the fluorination of a bis (chlorosulfonyl) imide with a fluorinating agent ZnF2 to form a zinc salt of bis (fluorosulfonyl) imide. Then, the zinc salt is contacted with an aqueous ammonia solution to form an ammonium salt of bis (fluorosulfonyl) imide. A cation exchange step is performed with LiOH to achieve LiFSI.
• This process has the drawback of using an aqueous solution, which has the effect of dissolving the LiFSI.
• the process includes additional extraction steps, which complicates the process and impacts production costs.
• this process for preparing LiFSI comprises the preparation of several intermediate compounds (zinc salt, ammonium salt).
• the accumulation of steps can cause a decrease in the final yields of LiFSI.
• the present invention relates to a process for preparing a compound of the following formula (II):
• R 1 represents F or an alkyl radical, linear or branched, substituted by at least one fluorine atom
• said process comprising a step of bringing an anhydrous stream F1 comprising ammonia (NH 3) into contact with a compound of formula (I):
• R 1 being as defined above.
• anhydrous stream is meant a stream comprising a water content of less than 800 ppm, preferably less than or equal to 500 ppm, and advantageously less than or equal to 200 ppm. .
• R 1 represents one of the following radicals: F, CF 3 , CHF2, CH 2 F, C2HF4, C2H2F 3 , C2H 3 F2, C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H4F 3 , C4F 9 , C4H2F 7 , C 4 H 4 F 5 , OR C 5 F11, R 1 preferably being F.
• the anhydrous stream F1 can be a liquid anhydrous stream or a gaseous anhydrous stream.
• anhydrous flow F1 When the anhydrous flow F1 is a liquid flow, it may be a flow comprising liquid ammonia (NH 3 ) or ammonia (NH 3 ) in solution in an organic solvent or a mixture of organic solvents .
• the organic solvent can be selected from the group consisting of esters, nitriles, ethers, amines, phosphines, and mixtures thereof.
• the organic solvent is preferably selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, acetonitrile, propionitrile, isobutyronitrile, glutaronitrile, dioxane, tetrahydrofuran, methanol, ethanol, propanol, butanol, and mixtures thereof.
• the organic solvent is butyl acetate.
• the method may comprise, prior to the aforementioned contacting step, a step of dissolving gaseous or liquid NH 3 in an organic solvent or a mixture of organic solvents as defined above, advantageously forming an anhydrous liquid stream F1 .
• the concentration of ammonia (NH 3 ) dissolved in an organic solvent or a mixture of organic solvents can be between 0.01 mol / L and the maximum solubility of ammonia in said organic solvent (s) ( s).
• the anhydrous stream F1 is a gas stream, it contains gaseous ammonia (NH 3 ).
• the aforementioned contacting step can be carried out at a temperature T ranging from 0 ° C to 40 ° C, preferably from 0 ° C to 30 ° C, and preferably from 2 ° C to 30 ° C.
• the aforementioned contacting step can be carried out at a pressure P of between 0.1 and 15 bar absolute.
• the molar ratio compound of formula (I): ammonia (NH 3 ) can be between 0.01 and 1, preferably between 0.1 and 0.5, and advantageously between 0.1 and 0.4.
• the compound of formula (I) above can be obtained by a process comprising a fluorination step of a compound of formula (A):
• R 2 represents one of the following radicals: Cl, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C3F7, C3H4F3, C3HF6, C4F9, C4H 2 F7, C4H4F5, C5F11, C6F13, C7F15, CeFu or C 9 F 19 , preferably R 2 representing Cl;
• the fluorinating agent can be chosen from the group consisting of HF (for example anhydrous HF), KF, ASF 3 , B1F 3 , ZnF 2 , SnF 2 , PbF 2 , CuF 2 , and mixtures thereof, the agent of fluorination being preferably HF, and even more preferably anhydrous HF.
• anhydrous HF THF containing less than 500 ppm of water, preferably less than 300 ppm of water, preferably less than 200 ppm of water.
• This step can be carried out in at least one SOI organic solvent.
• the SOI organic solvent preferably has a donor number between 1 and 70 and advantageously between 5 and 65.
• the donor index of a solvent represents the value - DH, DH being the enthalpy of the interaction between the solvent and antimony pentachloride (according to the method described in Journal of Solution Chemistry, vol. 13, no. 9, 1984).
• SOI organic solvent mention may in particular be made of esters, nitriles, dinitriles, ethers, diethers, amines, phosphines, and mixtures thereof.
• the SOI organic solvent is chosen from the group consisting of methyl acetate, ethyl acetate, butyl acetate, acetonitrile, propionitrile, isobutyronitrile, glutaronitrile , dioxane, tetrahydrofuran, triethylamine, tripropylamine, diethylisopropylamine, pyridine, trimethylphosphine, triethylphosphine, diethylisopropylphosphine, and mixtures thereof.
• the SOI organic solvent is dioxane or butyl acetate.
• the fluorination step can be carried out at a temperature of between 0 ° C.
• step b) is carried out at a temperature between 5 ° C and the boiling point of the SOI organic solvent (or of the mixture of SOI organic solvents), preferably between 20 ° C and the boiling point of the SOI.
• SOI organic solvent or mixture of SOI organic solvents.
• the fluorination step can be carried out at a pressure P, preferably between 0 and 16 bar abs.
• This step is preferably carried out by dissolving the compound of formula (A) in the SOI organic solvent, or the mixture of SOI organic solvents, prior to the step of reaction with the fluorinating agent, preferably with the Anhydrous HF.
• the molar ratio x between the fluorinating agent, preferably the anhydrous HF, and the compound of formula (A) used is preferably between 1 and 10, and advantageously between 1 and 5.
• the fluorination step can be carried out in a closed environment or in an open environment, preferably step b) is carried out in an open environment with in particular the release of HCl in gas form.
• the fluorination reaction typically leads to the formation of HCl, the majority of which can be degassed from the reaction medium (just like excess THF if the fluorinating agent is HF), for example by stripping with a neutral gas (such as than nitrogen, helium or argon).
• a neutral gas such as than nitrogen, helium or argon
• the compound of formula (I) can optionally be subjected to a distillation step.
• the step of bringing an anhydrous stream F1 into contact with a compound of formula (I) can be carried out with a compound of formula (I) resulting directly from the fluorination step or resulting from an additional distillation step of the composition obtained at the end of the fluorination step.
• the compound of formula (A) can be prepared by any means known to those skilled in the art, for example as described in WO2015 / 158979, W02009 / 123328, or alternatively by reaction between a chlorosulfonyl isocyanate with chlorosulfonic acid (US2013 / 331609).
• Compound (A) may also be available commercially.
• the present invention also relates to a process for preparing a compound of formula (III): F-SO2-N - SO2-R1 Li + (III) in which R 1 is as defined above, said process comprising the process for preparing a compound of formula (II) as defined above.
• the present invention relates to a process for preparing a compound of formula (III) comprising:
• a cation exchange step by bringing the compound of formula (II) into contact with a lithium salt, in particular selected from the group consisting of lithium fluorides, lithium chlorides, lithium carbonates, lithium hydroxides, lithium sulfates, lithium chlorates, lithium perchlorates, lithium nitrites, lithium nitrates, and mixtures thereof.
• a lithium salt in particular selected from the group consisting of lithium fluorides, lithium chlorides, lithium carbonates, lithium hydroxides, lithium sulfates, lithium chlorates, lithium perchlorates, lithium nitrites, lithium nitrates, and mixtures thereof.
• the aforementioned process may include an intermediate purification step of the compound of formula (II) prior to cation exchange step ii).
• Purification can include a filtration step, washing with an organic solvent, an extraction step, etc.
• Step ii) can be carried out in an organic solvent, preferably polar, or an aqueous solvent, such as, for example, water.
• polar organic solvents mention may for example be made of alcohols, nitriles, carbonates and their mixtures.
• alcohols for example, there may be mentioned methanol, ethanol, acetonitrile, dimethylcarbonate, ethylmethylcarbonate, and mixtures thereof.
• the lithium salt can be a solid lithium salt or a lithium salt in solution in at least one organic solvent.
• Reaction ii) can be carried out at a temperature between 0 ° C and the boiling point of the solvent used, preferably between 0 ° C and 50 ° C.
• reaction time of step ii) can be for example between 1 hour and 5 days, preferably between 1 hour and 1 day.
• the molar ratio between the lithium salt and the compound of formula (II) can be between 0.9 and 5.
• the above-mentioned process can comprise a step iii) of recovering the product of formula (III).
• the reaction medium can be filtered to remove the precipitate formed with the ammonium cation.
• the filtrate can then be concentrated to remove the solvent.
• a precipitate with the ammonium cation can form again and can be removed by filtration.
• Excess lithium salt can be removed by washing with water which can be performed after evaporation or directly on the solution of the compound of formula (III) in an organic solvent chosen from the following families: esters, ethers, chlorinated or aromatic solvents such as, for example, dichloromethane, acetonitrile, acetate ethyl, butyl acetate, diethyl ether, tetrahydrofuran.
• the solution of the compound of formula (III) obtained at the end of step ii) can be evaporated, for example by a thin-film evaporator or by an atomizer or by a rotary evaporator.
• the compound of formula (III) thus obtained can be dissolved in an amount of water which can vary between 4/1 and 1/1 of the total mass of the compound of formula (III) with solvent.
• the product dissolved in the aqueous solution can then be extracted using an organic solvent chosen from the following families: esters, ethers, chlorinated or aromatic solvents such as, for example, dichloromethane, ethyl acetate, butyl acetate, diethyl ether, tetrahydrofuran.
• the solution of the compound of formula (III) obtained can be washed with water.
• the washes can be multiple, ranging in particular from 2 to 10 with increasing or decreasing amounts during the washings.
• the mass quantities of water used during the wash (s) are between 1/10 and 2 times the mass of the product solution to be washed.
• the washed organic phase can then be evaporated in particular with a thin-film evaporator or an atomizer or a rotary evaporator.
• the compound of formula (III) obtained by the above-mentioned process can be subjected to at least one purification step. It can be purification well known to those skilled in the art such as, for example, liquid-liquid extractions, recrystallization, etc.
• the compound of formula (III) is selected from the following compounds: LiN (FS0 2) 2, UNSO2CF3SO2F, UNSO2C2F5SO2F, UNSO2CHF2SO2F, UNSO2CH2FSO2F, UNSO2C2HF4SO2F, UNSO2C2H2F3SO2F, UNSO2C2H3F2SO2F, UNSO2C 3 F 7 SO 2 F, UNSO2C 3 H2F 5 SO2F, UNSO2C 3 H4F 3 SO2F, UNSO2C4F 9 SO2F, UNSO2C4H2F 7 SO2F, UNSO2C4H4F 5 SO2F, LiNS02C 5 FiiS0 2 F, the compound of formula (III) preferably being LiN (FSC> 2) 2.
• an intermediate step for preparing a compound of formula (II) advantageously makes it possible to prepare a compound of formula (III) such as LiFSI, at low cost and with a high yield.
• this process advantageously makes it possible to avoid a step of neutralization, with an aqueous solution based on lithium, of the compound of formula (I) such as bis (fluorosulfonyl) imide which is unstable in aqueous solution, and therefore makes it possible to '' avoid the generation of degradation products likely to impact the performance of the final product.
• by “between x and y”, or “ranging from x to y”, is meant an interval in which the limits x and y are included.
• the temperature “between 30 and 100 ° C” includes in particular the values 30 ° C and 100 ° C.

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• 2019
  • 2019-05-22 FR FR1905385A patent/FR3096367B1/fr active Active
• 2020
  • 2020-05-19 EP EP20737249.1A patent/EP3972932A1/de active Pending
  • 2020-05-19 WO PCT/FR2020/050828 patent/WO2020234537A1/fr unknown
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