Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
• • 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
  • 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
• • 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
  • C07C303/42—Separation; Purification; Stabilisation; Use of additives
  • C07C303/44—Separation; Purification
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
• • 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 the preparation of imide salts containing a fluorosulfonyl group.
• Anions of sulfonylimide type 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 supercapacitors or in the field of liquids ionic.
• LiPF 6 LiPF 6
• this salt shows numerous disadvantages such as limited thermal stability, sensitivity to hydrolysis and therefore lower battery safety.
• new salts having the FSO 2 group have been studied and have demonstrated many advantages such as better ionic conductivity and resistance to hydrolysis.
• LiFSI LiN (FSO 2 ) 2
• LiFSI LiN (FSO 2 ) 2
• the present invention relates to a process for preparing a compound of the following formula:
• R 2 represents one of the following radicals: F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7, C 3 H 4 F 3, C 3 HF 6, C 4 Fg, C 4 H 2 F 7, C 4 HF 5, C5F1 1, CeF I 3, C 7 F 15, C S FI 7 OR C9F19, of preferably R 2 representing F;
• M represents a monovalent or divalent cation, preferably M represents a monovalent cation
• said method comprising:
• R 1 being preferably Cl; with at least one fluorinating agent, preferably in the presence of at least one SOI organic solvent;
• step c) of distillation of the composition obtained in step b), said composition comprising a compound of formula (II) below:
• the process according to the invention may comprise a possible stage d) of dissolving the composition obtained in stage c) in an organic solvent S02.
• the method according to the invention comprises a step e) of bringing the composition obtained in step c) or step d) into contact with a composition comprising at least one alkali metal or alkaline earth metal salt. , allowing to lead to a compound of formula (III) below: R 2 - (S0 2 ) -NM- (S0 2 ) -F (III)
• R 2 and M being as defined above.
• the method according to the invention may comprise a cation exchange step f) for converting a compound of formula (III) into another compound of formula (III), but for which M is different.
• the present invention relates to a process for preparing a compound of formula (III) as defined above, said process comprising:
• step a) comprising the reaction of a sulphonamide of formula (A) below:
• R 0 represents one of the following radicals: OH, Cl, F, CF 3 , CHF 2 , CH 2 F,
• Ri 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 2J C 2 F 5, C 3 F 7J C 3 H 4 F 3J C 3 HF 6, C 4 Fg, C 4 H 2 F 7, C 4 H 4 F 5, C 5 F 11, CeF I3, C 7 F 15, C 8 FI 7 OR C 9 F 19, R 1 preferably being Cl;
• step c) of distillation of the composition obtained in step b), said composition comprising a compound of formula (II) below:
• the process according to the invention advantageously makes it possible to remedy at least one of the disadvantages of the existing processes. It advantageously allows:
• the aforementioned method further comprises a step a), prior to step b), comprising the reaction of a sulfamide of formula (A) below:
• the compound (A) is that in which R 0 represents OH.
• Step a) can be performed:
• the sulfur-containing agent may be selected from the group consisting of chlorosulfonic acid (CIS0 3 H), sulfuric acid, oleum, and mixtures thereof.
• the chlorinating agent may be selected from the group consisting of thionyl chloride (SOCI 2 ), oxalyl chloride (COCI) 2 , phosphorus pentachloride (PCI 5 ), phosphonyl trichloride (PCI) 3 ), phosphoryl trichloride (POCI 3 ), and mixtures thereof.
• the chlorinating agent is thionyl chloride.
• the chlorination step a) can be carried out in the presence of a catalyst, such as, for example, chosen from a tertiary amine (such as methylamine, triethylamine or diethylmethylamine); pyridine; and 2,6-lutidine.
• a catalyst such as, for example, chosen from a tertiary amine (such as methylamine, triethylamine or diethylmethylamine); pyridine; and 2,6-lutidine.
• the molar ratio between the sulfuric acid and the compound (A) may be between 0.7 and 5, preferably between 0.9 and 5.
• the molar ratio between the chlorinating agent and the compound (A) may be between 2 and 10, preferably between 2 and 5.
• the sulfur-containing agent is chlorosulphonic acid
• the sulfur-containing agent is sulfuric acid (or oleum)
• the molar ratio of sulfuric acid (or oleum) to the compound (A) is between 0.7 and 5.
• the sulfur-containing agent is sulfuric acid (or oleum)
• Step a) advantageously makes it possible to form a compound of formula (I):
• R 1 is as defined above, and in particular wherein R 1 is Cl.
• the process according to the invention comprises a step b) of fluorination of a compound of formula (I) below:
• R 1 represents one of the following radicals: Cl, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , R 1 (S0 2 ) -NH- (S0 2 ) -CI (I)
• Step b) in particular allows the fluorination of the compound of formula (I) into a compound of formula (II):
• R 2 represents F, CF 3 , CHF 2 , or CH 2 F. It is particularly preferred that R 2 represents F.
• the fluorinating agent is chosen from the group consisting of HF (preferably anhydrous HF), KF, AsF 3 , BiF 3 , ZnF 2 , SnF 2 , PbF 2 , CuF 2 , and mixtures thereof. , the fluorinating agent preferably being HF, and even more preferably anhydrous HF.
• anhydrous HF means THF containing less than 500 ppm water, preferably less than 300 ppm water, preferably less than 200 ppm water.
• Step b) of the process is preferably carried out in at least one SOI organic solvent.
• the organic solvent SOI preferably has a donor number of between 1 and 70 and advantageously of 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).
• organic solvent SOI there may be mentioned in particular esters, nitriles, dinitriles, ethers, diethers, amines, phosphines, and mixtures thereof.
• the organic solvent SOI is selected 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 organic solvent SOI is dioxane.
• Step b) can be carried out at a temperature of between 0 ° C. and the boiling temperature of the SOI organic solvent (or of the SOI organic solvent mixture).
• step b) is carried out at a temperature of between 5 ° C. and the boiling temperature of the organic solvent SOI (or the mixture of organic solvents SOI), preferably between 20 ° C. and the boiling temperature of SOI organic solvent (or SOI organic solvent mixture).
• Step b) preferably with anhydrous hydrofluoric acid, can be carried out at a pressure P, preferably between 0 and 16 bar abs.
• This step b) is preferably carried out by dissolving the compound of formula (I) in the organic solvent SOI, or the mixture of organic solvents SOI, before the reaction step with the fluorinating agent, preferably with Anhydrous THF.
• the weight ratio between the compound of formula (I) and the organic solvent SOI, or the mixture of organic solvents SOI, is preferably between 0.001 and 10, and advantageously between 0.005 and 5.
• anhydrous THF is introduced into the reaction medium, preferably in gaseous form.
• the molar ratio x between the fluorinating agent, preferably anhydrous HF, and the compound of formula (I) used is preferably between 1 and 10, and advantageously between 1 and 5.
• reaction step with the fluorinating agent preferably anhydrous GI-IF
• step b) is carried out in an open medium, in particular with the release of HCl in the form of gas.
• the fluorination reaction typically leads to the formation of HCl, the majority of which can be degassed from the reaction medium (just like the excess HF if the fluorination agent is HF), for example by stripping with a neutral gas. (such as nitrogen, helium or argon).
• a neutral gas such as nitrogen, helium or argon.
• composition obtained at the end of step b) can be stored in an HF-resistant container.
• the composition obtained in step b) may comprise HF (it is in particular unreacted HF), the compound of formula (II) mentioned above, the SOI solvent (such as, for example, dioxane), and optionally HCl, and / or possibly heavy compounds.
• the process according to the invention comprises a step c) of distillation of the composition obtained in step b), said composition comprising a compound of formula (II) below:
• step c) of distillation of the composition obtained in step b) makes it possible to form and recover:
• a first stream F1 comprising HF, optionally the organic solvent SOI and / or optionally HCl, preferably at the top of the distillation column, said stream F1 being gaseous or liquid;
• a second stream F2 comprising the compound of formula (II), and optionally heavy compounds, preferably at the bottom of the distillation column, said stream F2 being preferably liquid.
• the stream F2 comprises heavy compounds
• it can be subjected to a further distillation step in a second distillation column, to form and recover: a stream F2-1 comprising the compound of formula (II) free of heavy compounds, preferably at the top of the distillation column, said stream F2-1 being preferably liquid, a stream F2-2 comprising the heavy compounds and the compound of formula (II), preferably at the bottom of the distillation column, said F2-2 flux containing less than 10% by weight of the compound of formula (II) contained in the composition obtained in step b), preferably less 7% by weight, and preferably less than 5% by weight, said F2-2 flux being preferably liquid.
• step c) of distillation of the composition obtained in step b) makes it possible to form and recover, thanks to the use of two distillation columns: a first stream F1 comprising HF, optionally the organic solvent SOI and / or optionally HCl at the top of the first distillation column, said stream F1 being gaseous or liquid;
• a second stream F2 comprising the compound of formula (II), and optionally heavy compounds at the bottom of the first distillation column, said stream F2 preferably being liquid;
• stream F2 being subjected to a distillation step in a second distillation column, to form and recover: a stream F2-1 comprising the compound of formula (II) free of heavy compounds at the head of the second distillation column, said stream F2-1 being preferably liquid,
• a stream F2-2 comprising the heavy compounds and the compound of formula (II), at the bottom of the second distillation column, said stream F2-2 containing less than 10% by weight of the compound of formula (II) contained in the composition obtained in step b), preferably less than 7% by weight, and preferably less than 5% by weight, said F2-2 flux preferably being liquid.
• step c) of distillation of the composition obtained in step b) makes it possible to form and recover: a first stream F'1 comprising HF, optionally the organic solvent SOI and / or optionally HCl, preferably at the top of the distillation column, said stream F'1 being gaseous or liquid;
• a second stream F'2 comprising the compound of formula (II), preferably recovered by lateral withdrawal, said stream F'2 being preferably liquid; a third stream F'3 comprising heavy metals and the compound of formula (II), preferably at the bottom of the distillation column, said stream F'3 containing less than 10% by weight of the compound of formula (II) contained in the composition obtained in step b), preferably less than 7% by weight, and preferably less than 5% by weight, said F'3 flux being preferably liquid.
• the distillation column may contain at least one tray.
• the distillation step c) may be carried out at a pressure ranging from 0 to 5 bar abs, preferably from 0 to 3 bar abs, preferably from 0 to 2 bar abs, and advantageously from 0 to 1 bar abs.
• the distillation step c) can be carried out:
• a temperature at the bottom of the distillation column ranging from 150 ° C. to 200 ° C., preferably from 160 ° C. to 180 ° C., and preferably from 165 ° C. to 175 ° C., at a pressure of 1 bar abs; or
• the distillation step c) can be carried out in any conventional device. It may be a distillation device comprising a distillation column, a boiler and a condenser.
• the distillation column may comprise:
• At least one lining such as for example a loose lining and / or a structured lining,
• distillation column typically depends on the nature of the compounds to be separated. Typically, depending on the flows used, the distillation column can have any type of diameter: small (less than or equal to 1 meter) or high (greater than 1 meter).
• the material of the distillation column, its internal constituents (packing and / or trays), the boiler, and / or the condenser is advantageously chosen from corrosion-resistant materials, due to the potential presence of HF and / or HCl in the composition subjected to distillation.
• the corrosion-resistant materials can be selected from enamelled steels, nickel, titanium, chromium, graphite, silicon carbides, nickel-based alloys, cobalt-based alloys, alloy-based alloys, chromium, steels coated partially or totally by a fluoropolymer protective coating (such as for example PVDF: polyvinylidene fluoride, PTFE: polytetrafluoroethylene, PFA: copolymer of C 2 F 4 and perfluorinated vinyl ether, FEP: copolymer of C 2 F 4 and C 3 F 6, ETFE: copolymer of ethylene and tetrafluoroethylene, or FKM: copolymer of hexafluoropropylene and difluoroethylene).
• a fluoropolymer protective coating such as for example PVDF: polyvinylidene fluoride, PTFE: polytetrafluoroethylene, PFA: copolymer of C 2 F 4 and perfluorinated vinyl ether, F
• the nickel-based alloys are preferably alloys comprising at least 40% by weight of nickel, preferably at least 50% by weight of nickel relative to the total weight of the alloy.
• alloys comprising at least 40% by weight of nickel, preferably at least 50% by weight of nickel relative to the total weight of the alloy.
• Flows F1 and F'1 can comprise HF, HCl, SOI organic solvent (in particular dioxane).
• the flow F'1 comprises from 2 to 70% by weight of HF, preferably from 5 to 60% by weight of HF relative to the total weight of the F'1 flux, and from 30% to 98% by weight. % by weight of organic solvent SOI, preferably from 40% to 95% by weight of SOI, relative to the total weight of the flow F'1.
• the stream F2 comprises from 50 to 100% by weight of compound of formula (II), preferably from 70 to 99% by weight of compound of formula (II) relative to the total weight of stream F2.
• the flow F'2 comprises from 50 to 100% by weight of compound of formula (II), preferably from 70 to 99% by weight of compound of formula (II) relative to the total weight of the stream.
• the stream F2-1 comprises from 50 to 100% by weight of compound of formula (II), preferably from 70 to 99% by weight of compound of formula (II) relative to the total weight of the stream. F2-1.
• Step c) advantageously allows the recovery of a compound of formula (II) having a high purity.
• the use of a compound of formula (II) of high purity advantageously makes it possible to prepare a compound of formula (III), in particular LiFSI, having a high purity, without requiring additional purification steps.
• the method according to the invention comprises a step d) of dissolving the composition obtained in step c) in an organic solvent SO 2, said solvent SO 2 being preferably polar aprotic.
• the organic solvent S02 may be a water-miscible solvent.
• solvent miscible with water a solvent does not form a macroscopic phase separation.
• the organic solvent SO2 may be selected from the group consisting of ethers, diethers, nitriles, amines, carbonates or phosphines.
• the organic solvent S02 is selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, acetonitrile, propionitrile, isobutyronitrile, glutaronitrile , dioxane, tetrahydrofuran, triethylamine, tripropylamine, diethylisopropylamine, pyridine, diethylcarbonate, dimethylcarbonate, methylethylcarbonate, ethylene carbonate, trimethylphosphine, triethylphosphine, diethylisopropylphosphine and mixtures thereof , the solvent SO 2 preferably being dioxane or butyl acetate or acetonitrile, and advantageously dioxane.
• step d) comprises adding said SO 2 solvent in the composition obtained in step b) or in step c).
• step d) comprises in particular the placing in solution of the flow F2 (or F2-1 flux or F'2 flux) in an organic solvent S02.
• the method according to the invention comprises a step e) of bringing the composition obtained in step c) or step d) into contact with a composition comprising at least one alkali metal salt or alkaline earth metal, to lead to a compound of formula (III) below:
• R 2 and M being as defined above.
• Step e) advantageously makes it possible to convert the compound of formula (II) into a compound of formula (III) mentioned above:
• R 2 represents one of the following radicals: F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 4 F 3 , C 3 HF 6 , C 4 F 6 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 1 1, C 3 F 3 , C 7 F 15, C 8 F 1 7 or C9F19, where R 2 is preferably F; and
• M represents a monovalent cation, preferably K + or Li + or Na + , or a divalent cation, M preferably representing a monovalent cation.
• step e) can be carried out from the composition obtained in step c) (flux F2, or flux F2-1 or flux F'2), or from the composition obtained in step d ) or after any intermediate step between step c) and step e).
• the composition comprising at least one alkali metal or alkaline earth metal salt is an aqueous composition, preferably an aqueous suspension or an aqueous solution.
• the composition comprising at least one alkali metal or alkaline earth metal salt is a solid composition, preferably the composition consists of at least one alkali metal or alkaline earth metal salt.
• the contacting step may correspond to the addition of the composition obtained in step c) or step d) in the composition comprising at least one alkali metal or alkaline earth metal salt, or the reverse.
• the composition obtained in step c) or d) is added to the composition comprising at least one alkali metal or alkaline earth metal salt.
• Step e) can be carried out in a reactor, preferably comprising at least one stirring system.
• the alkali or alkaline earth metal salt may be a salt of the cation M.
• the alkali metal or alkaline earth metal salt is selected from the group consisting of MOH, MOH, H 2 O, MHCO 3 , M 2 CO 3 , MCI, M (OH) 2 , M (OH) 2 , H 2 O, M (HC0 3 ) 2 , MC0 3 , MCI 2 , and mixtures thereof, M being as defined above.
• the alkali or alkaline earth metal salt is selected from the group consisting of MOH, MOH, H 2 O, MHCO 3 , M 2 CO 3 , MCI, and mixtures thereof.
• the alkali metal or alkaline earth metal salt is selected from the group consisting of LiOH, LiOH, H 2 O, LiHCO 3 , U 2 CO 3 , LiCl, KOH, KOH, H 2 O, KHCO 3 , K 2 CO 3. , KOH, NaOH, NaOH, H 2 O, NaHCO 3 , Na 2 CO 3 , NaCl, and mixtures thereof, the salt being preferably a potassium salt, and advantageously K 2 CO 3 .
• composition when it is an aqueous composition comprising at least one alkali metal or alkaline earth metal salt, may be prepared by any conventional means for preparing an aqueous alkaline composition. It may for example be the dissolution of the alkali metal or alkaline earth metal salt in ultrapure or deionized water, with stirring.
• the aforementioned method comprises a step e) comprising the addition of the composition obtained in step c) or step d), said composition comprising a compound of formula (II) mentioned above:
• R 2 being as defined above, and preferably R 2 representing F,
• aqueous composition comprising at least one potassium salt or a lithium salt, preferably a potassium salt.
• an analysis of the total acidity of the mixture to be neutralized can typically be carried out.
• step e) is such that:
• the molar ratio of the alkali metal or alkaline earth metal salt divided by the number of basicities of said salt relative to the compound of formula (II) is greater than or equal to 1, preferably less than 5, preferably less than 3, preferably between 1 and 2; and or
• the mass ratio of the alkali metal or alkaline earth metal salt to the mass of water in the aqueous composition is between 0.1 and 2, preferably between 0.2 and 1, preferably between 0.3 and 0.7.
• the salts Li 2 CO 3 and K 2 CO 3 each have a number of basicities equal to 2.
• Step e) of the process according to the invention may be carried out at a temperature of less than or equal to 40 ° C, preferably less than or equal to 30 ° C, preferably less than or equal to 20 ° C, and in particular less than or equal to 15 ° C.
• the method according to the invention comprises an additional step of filtering the composition obtained in step e), resulting in a filtrate F and a cake G.
• the compound of formula (III) prepared may be contained in the filtrate F and / or in the cake G.
• the filtrate F can be subjected to at least one extraction step with an organic solvent SO 3 typically poorly soluble in water, in order to extract the compound of formula (III) mentioned above in an organic phase.
• the extraction step typically leads to the separation of an aqueous phase and an organic phase.
• “poorly soluble in water” means a solvent whose solubility in water is less than 5% by weight.
• the organic solvent SO 3 mentioned above is in particular chosen from the following families: esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and mixtures thereof.
• the organic solvent SO 3 is chosen from dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran and diethyl ether, and mixtures thereof.
• the organic solvent SO 3 is butyl acetate.
• the mass quantity of organic solvent used can vary between 1/6 and 1 times the weight of the filtrate F.
• the number of extractions can be between 2 and 10.
• the organic phase resulting from the extraction (s) has a mass content of compound of formula (III) ranging from 5% to 40% by weight.
• the separated organic phase (obtained after the extraction) can then be concentrated to reach a concentration of compound of formula (III) of between 30% and 60%, preferably between 40% and 50% by weight, concentration that can be achieved by any means of evaporation known to those skilled in the art.
• the aforementioned cake G can be washed with an organic solvent S04 selected from the following families: esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and mixtures thereof.
• the organic solvent SO 4 is chosen from dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran, acetonitrile, diethyl ether, and mixtures thereof.
• the organic solvent SO 4 is butyl acetate.
• the mass quantity of organic solvent S04 used may vary between 1 and 10 times the weight of the cake.
• the total quantity of organic solvent S04 intended for washing can be used in one go or in several times, in particular in order to optimize the dissolution of the compound of formula (III).
• the organic phase, resulting from washing (s) cake G has a mass content of compound of formula (III) ranging from 5% to 20% by weight.
• the separated organic phase resulting from the washing (s) of the cake G can then be concentrated to reach a concentration of compound of formula (III) of between 30% and 60%, preferably between 40% and 50% by weight. said concentration can be achieved by any means of evaporation known to those skilled in the art.
• the organic phases resulting from the extraction (s) of the filtrate F and the washing (s) of the cake G can be collected together, before the concentration step.
• the process according to the invention may comprise, after step e), a cation exchange step f) for converting a compound of formula (III) into another compound of formula (III), but for which M represents a cation monovalent different.
• this step comprises the reaction between a compound of formula (III) obtained in step e) above:
• R 2 represents one of the following radicals: F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 4 F 3 , C 3 HF 6 , C 4 F 6 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 1 1, C 3 F 13 , C 7 F 15, C 8 F 1 7 OR
• M represents a monovalent or divalent cation, preferably a monovalent cation, with an alkali metal or alkaline earth metal salt whose cation is different from M (for example M ').
• the process may comprise a step f) of cation exchange of this compound with a metal salt alkali or alkaline earth metal whose cation is not K + , for example with a lithium salt.
• step e) leads to a compound of formula (III-A):
• R 2 represents one of the following radicals: F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 4 F 3 , C 3 HF 6 , C 4 F 6 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 1 1, C 8 F 13 , C 7 F 15, C 8 F 1 7 OR
• - M represents a monovalent cation, or divalent, preferably monovalent
• the process may comprise a cation exchange step (f) of the compound of formula (III-A) to a compound of formula (III-B):
• R 2 represents one of the following radicals: F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7J C 3 H 4 F 3 J C 3 HF 6 , C 4 F 1 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 1 1, C 8 F 13 , C 7 F 15, C 8 F 1 7 OR
• M ' represents a monovalent cation different from M.
• the process according to the invention may further comprise a step of purifying the compound of formula (III) mentioned above.
• This step can be performed at the end of step e) or after step f).
• Step g) of purification of the compound of formula (III) can be carried out by any known conventional method. This may be for example an extraction method, a washing method with solvents, a reprecipitation method, a recrystallization method, or their combination.
• the compound of formula (III) may be in the form of a composition comprising from 30% to 95% by weight of compound of formula (III) relative to the total weight of said composition.
• step g) is a crystallization step of the compound of formula (III) mentioned above.
• the compound of formula (III) mentioned above is cold-crystallized, in particular at a temperature of less than or equal to 25 ° C.
• step g) the crystallization of the compound of formula (III) is carried out in an organic solvent S05 ("crystallization solvent") chosen from chlorinated solvents, such as, for example, dichloromethane, and solvents aromatic compounds, such as, for example, toluene, in particular at a temperature of less than or equal to 25.degree.
• organic solvent S05 chlorinated solvents, such as, for example, dichloromethane, and solvents aromatic compounds, such as, for example, toluene, in particular at a temperature of less than or equal to 25.degree.
• the compound of formula (III) crystallized at the end of step d) is recovered by filtration.
• the crystallization step is preferably carried out on a composition comprising between 75% and 90% by weight of the compound of formula (III).
• the composition obtained the result of step e) or f) can be concentrated to obtain a solution corresponding to the aforementioned composition. Concentration can be done by any conventional means of concentration. It can in particular be carried out under reduced pressure of between 40mbars and 0.01 mbar at a temperature below 70 ° C, preferably below 50 ° C, preferably below 40 ° C. It can be preferably performed according to the conditions of step v) described below.
• step g) comprises the following steps: i) optionally dissolving the compound of formula (III) in an organic solvent S'1;
• Step g) may not comprise step i) mentioned above, if the compound of formula (III) obtained in step e) or in step f) already comprises an organic solvent (such as for example SO 3 and / or S04).
• an organic solvent such as for example SO 3 and / or S04.
• step ii) comprises in particular the addition of deionized water to the solution of the compound of formula (III) in the abovementioned organic solvent S'1, to allow the dissolution of said of formula (III), and the extraction of said of formula (III) in water (aqueous phase).
• the extraction can be carried out by any known extraction means.
• the extraction typically allows the separation of an aqueous phase (aqueous solution of said salt in this case) and an organic phase.
• step ii) can be repeated at least once, for example three times.
• a quantity of deionized water corresponding to half of the mass of the initial solution can be added, then an amount equal to about 1/3 of the mass of the initial solution during the second extraction, then a amount equal to about 1/4 of the mass of the initial solution during the third extraction.
• step ii) is such that the mass of deionized water is greater than or equal to one third, preferably greater than or equal to half, of the mass of the initial solution of the compound of formula (III) in the organic solvent S'1 (in the case of a single extraction, or for the first extraction only if step ii) is repeated at least once).
• the extracted aqueous phases can be combined together to form a single aqueous solution.
• step ii) an aqueous solution of compound of formula (III) is obtained in particular.
• the mass content of compound of formula (III) in the aqueous solution is between 5% and 35%, preferably between 10% and 25%, relative to the total mass of the solution.
• step g) comprises a concentration step iii) between step ii) and step iv), preferably to obtain an aqueous solution of the compound of formula (III) comprising a mass content of compound of formula (III) 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 of less than 50 mbar abs (preferably less than 30 mbar abs), and in particular at a temperature of between 25 ° C and 60 ° C, preferably between 25 ° C and 500, preferably between 25 ° C and 40 ° C, for example at 40 ° C.
• the compound of formula (III), contained in the aqueous solution obtained at the end of step ii), and of a possible concentration step iii) or of any other intermediate step, can then be recovered by extraction. with an organic solvent S'2, said solvent S'2 being able to form preferably an azeotrope with water (step iv).
• Stage iv) of the conduit in particular, after extraction, with an organic phase, saturated with water, containing the compound of formula (III) (it is a solution of compound of formula (III) in the organic solvent S'2, said solution being saturated with water).
• the extraction typically allows the separation of an aqueous phase and an organic phase (solution of the compound of formula (III) in the solvent S'2 in the present case).
• Stage iv) advantageously makes it possible to obtain an aqueous phase and an organic phase, which are separated.
• the organic solvent S'2 is selected from the group consisting of esters, nitriles, ethers, carbonates, chlorinated solvents, aromatic solvents, and mixtures thereof.
• the solvent S'2 is chosen from ethers, esters, and mixtures thereof.
• the solvent S'2 is selected from methyl-t-butyl ether, cyclopentylmethyl ether, ethyl acetate, propyl acetate, butyl acetate, dichloromethane, tetrahydrofuran, acetonitrile, diethyl ether, and mixtures thereof.
• the solvent S'2 is selected from methyl-t-butyl ether, cyclopentylmethyl ether, ethyl acetate, propyl acetate, butyl acetate, and mixtures thereof.
• the organic solvent S'2 is butyl acetate.
• the extraction step iv) 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 v).
• the mass quantity of organic solvent used can vary between 1/6 and 1 times the mass of the aqueous phase.
• the weight ratio organic solvent S'2 / water, during an extraction of step iv) varies from 1/6 to 1/1, the number of extractions varying in particular from 2 to 10.
• the organic solvent S'2 is added to the aqueous solution resulting from step ii) (and from possible step iii).
• Step g) may comprise a pre-concentration step between step iv) and step v), preferably to obtain a solution of the compound of formula (III) in the organic solvent S ' 2 comprising a mass content of compound of formula (III) of between 20% and 60%, and preferably between 30% and 50% by weight relative to the total mass of the solution.
• the pre-concentration step may be carried out at a temperature ranging from 25 ° C. to 60 ° C., preferably from 25 ° C. to 45 ° C., optionally under reduced pressure, for example at a pressure of less than 50 mbar abs, in particular at a pressure of less than 30 mbar abs.
• the pre-concentration step is preferably carried out by a rotary evaporator under reduced pressure, in particular at 40 ° C. and at a pressure of less than 30 mbar abs.
• the concentration step v) can be carried out at a pressure of between 10 -2 mbar abs and 5 mbar abs, preferably between 5.10 -2 mbar abs and 2 mbar abs, preferably between 5.10 1 and 2 mbar abs, even more preferably between 0.1 and 1 mbar abs, and in particular between 0.4 and 0.6 mbar abs.
• step v) is carried out at 0.5 mbar abs or at 0.1 mbar.
• step v) 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 50 ° C and 70 ° C.
• step v) is carried out with a residence time of less than or equal to 15 minutes, preferably less than 10 minutes, and preferably less than or equal to 5 minutes and advantageously less than or equal to 3 minutes.
• the term “residence time” means the time that elapses between the entry of the solution of the compound of formula (III) (in particular obtained at the end of of step iv) above) in the evaporator and the outlet of the first drop of the solution.
• the temperature of the condenser of the short-path thin-film evaporator is between -50 ° to 5 ° C., preferably between -35 ° C. and 5 ° C. In particular, the temperature of the condenser is -5 ° C.
• the aforementioned short-path thin-film evaporators are also known as "Wiped film short path” (WFSP). They are typically so called because the vapors generated during evaporation make a “short trip" (short distance) before being condensed to the condenser.
• WFSP Wiped film short path
• evaporators marketed by the companies Buss SMS Ganzler ex Luwa AG, UIC Gmbh or VTA Process.
• short-path thin-film evaporators may include a solvent vapor condenser positioned within the apparatus itself (particularly in the center of the apparatus), unlike other types of film evaporators. thin (which are not short path) in which the condenser is located outside the device.
• the formation of a thin film of product to be distilled on the internal hot wall of the evaporator can typically be provided by continuously spreading on the evaporation surface by mechanical means. specified below.
• the evaporator may in particular be provided at its center, an axial rotor on which are mounted the mechanical means that allow the formation of the film on the wall.
• They may be rotors equipped with fixed blades: three-blade or four-blade lobed rotors in flexible or rigid materials, distributed over the entire height of the rotor or rotors equipped with moving blades, pallets, scrapers, guided rubbers.
• the rotor may be constituted by a succession of articulated pallets on pivot mounted on a shaft or axis via radial supports.
• Other rotors may be equipped with mobile rollers mounted on secondary axes and said rollers are pressed on the wall by centrifugation.
• the rotational speed of the rotor which depends on the size of the apparatus can be readily determined by those skilled in the art.
• the various mobiles can be made of various materials, for example metal, steel, alloy steel (stainless steel), aluminum, or polymers, for example PTFE polytetrafluoroethylene or glass materials (enamel); metallic materials coated with polymeric materials.
• the method according to the invention may comprise intermediate steps between the various steps of the aforementioned process.
• the steps a), b), c), and optionally d), and e) are sequential.
• the method according to the invention comprises:
• step a) comprising the reaction of a sulphonamide of formula (A) below:
• R 1 represents one of the following radicals: Cl, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 ,
• a first stream F1 comprising HF, the organic solvent SOI and optionally HCl, preferably at the top of the distillation column, said stream being gaseous or liquid;
• a second stream F2 comprising the compound of formula (II) mentioned above, and possibly heavy compounds, preferably at the bottom of the distillation column, said stream F2 preferably being liquid;
• the method according to the present invention is particularly useful for making the compounds of formula (III) include: LiN (S0 2 F) 2, LiNS0 2 CF 3 S0 2 F, UNS0 2 C 2 F 5 S0 2 F, UNS0 2 CF 2 0CF 3 S0 2 F, UNS0 2 C 3 HF 6 S0 2 F, LiNSO 2 C 4 F 9 S0 2 F, LiNSO 2 C 5 Fi 2 SO 2 F, UNSO 2 C 6 F 13 S0 2 F, LiNSO 2 C 7 F 15 S0 2 F, LiNS0 2 C 8 F 17 S0 2 F, LiNS0 2 C 9 F 19 S0 2 F, NaN (S0 2 F) 2, NaNS0 2 CF 3 S0 2 F, NaNS0 2 C 2 F 5 S0 2 F, NaNS0 2 CF 2 0CF 3 S0 2 F, NaNSO 2 C 3 HF 6 S0 2 F, NaNSO 2 C 4 F 9 S0 2 F, NaNSO 2 C 5 F 1 1 S0 2 F, NaN
• the process according to the invention is a process for the preparation of LiN (SO 2 F) 2 (LiFSI).
• lithium salt of bis (fluorosulfonyl) imide lithium salt of bis (fluorosulfonyl) imide
• lithium bis (sulfonyl) imide lithium bis (fluorosulfonyl) imide
• LiFSI lithium bis (sulfonyl) imide
• LiN (SO 2 F) 2 lithium bis (fluorosulfonyl) imide
• the process according to the invention advantageously leads to a compound of formula (III), and in particular to LiFSI, having a high purity, in particular at least 99.5% by weight, advantageously at least 99.95% in weight.
• ppm means ppm by weight.
• the present invention also relates to the use of the compound obtained by the process according to the invention in Li-ion batteries, in particular in electrolytes of Li-ion batteries.
• they may be Li-ion batteries of mobile devices (eg mobile phones, cameras, tablets or laptops), or electric vehicles, or renewable energy storage (such as than photovoltaics or wind energy).
• mobile devices eg mobile phones, cameras, tablets or laptops
• electric vehicles e.g. electric vehicles, or renewable energy storage (such as than photovoltaics or wind energy).
• renewable energy storage such as than photovoltaics or wind energy.
• between x and y or “ranging from x to y” means an interval in which the terminals x and y are included.
• the temperature "between -20 and 80 ° C” includes in particular the values -20 ° C and 80 ° C. All the embodiments described above can be combined with each other. In particular, each embodiment of any step of the method of the invention may be combined with another particular embodiment.
• HCISI bis (chlorosulfonyl) imide
• the mixture obtained is introduced into a reactor equipped with a vacuum distillation column connected to a dry ice trap.
• the pressure is set at 12 mbar.
• a first distillation fraction is obtained between room temperature and 36 ° C (vapor temperature).
• a second fraction distills between 48 ° C and 57 ° C. The distillation is then stopped.
• This second fraction consists of bis (fluorosulfonyl) imide (HFSI) (NMR analysis) at 99% purity and represents 53 g, a yield of 58%.
• the NMR spectra and quantifications were carried out on a Bruker AV 400 spectrometer, at 376.47 MHz for 19 F, on a 5 mm probe of BBFO + type.
• reaction medium is recovered and filtered to remove the excess lithium carbonate.
• the cake is washed with 100 ml of butyl acetate.
• LiFSI is recovered in solution, whose NMR analysis does not detect any cleavage products and whose ion chromatography analysis does not detect sulphate, potassium or sodium.

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