Classifications

• • 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
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4242—Regeneration of electrolyte or reactants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
• • 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
• • 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
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • 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
  • H01M2300/0085—Immobilising or gelification of 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 purifying an ionic electrolyte containing at least one alkaline earth salt.
• the purification is carried out by contacting the ionic electrolyte with at least one calcium salt.
• the ionic electrolytes thus purified are in particular of liquid type, gel polymer, molten salt or a mixture of at least two of these.
• the method of the invention allows more particularly to achieve a high dehydration treated electrolytes.
• the invention is particularly applicable to the preparation of electrolytic solutions of mixing and purified type.
• These solutions contain at least one salt of an alkaline earth element, such as a lithium salt, dissolved in at least one carbonate-type solvent such as ethylene carbonate (EC) or propylene carbonate (PC).
• EC ethylene carbonate
• PC propylene carbonate
• the process of the invention can also be used for the purification of impure lithium salts.
• the method of the invention thus makes it possible in particular to obtain electrolytic solutions of ionic conductive type and which have a low residual water content which may be less than 150 ppm of water.
• the method also makes it possible in particular to obtain purified lithium salts with less than 100 ppm, those whose H 2 O content is less than or equal to 20 ppm are new and are part of the present invention.
• the purified electrolytes obtained by the processes of the invention in particular the anhydrous solutions thus obtained with a water content of less than or equal to 20 ppm per liter of solution electrolyte, are new because of their original intrinsic characteristics and are also part of the invention.
• the electrochemical generators of the invention which incorporate a purified electrolyte of the invention and / or a purified lithium salt of the invention, have in particular an exceptional storage stability, they are new and also constitute an object of the invention. 'invention.
• Ionic-type electrolytic solutions are conventionally prepared by mixing specific amounts of a salt, for example an alkaline-earth salt, solvents and optionally a polymer when a gel-like consistency is desired, which is useful in particular. in the preparation of Li-ion or Li-metal batteries, to obtain a high energy density.
• a salt for example an alkaline-earth salt
• solvents for example an alkaline-earth salt
• polymer when a gel-like consistency is desired, which is useful in particular.
• Li-ion or Li-metal batteries to obtain a high energy density.
• LiPF 6 + EC-DEC electrolytes are used in commercial batteries. Aging electrolytes as a function of time generates water. The storage of electrolytes, in the long term, contaminates the latter by the formation of water. When the amount of water in the electrolyte exceeds 50 ppm, the performance of the battery is deteriorated, thus the service life is reduced and the undesirable phenomenon of self-discharge is increased.
• the water content is very critical, because the presence of water in the electrolyte is also at the origin of the formation, in particular:
• the water reduces the electrolyte and is the cause of the formation of a passivation film on the electrodes, this reaction is accompanied by the formation of gas and makes the battery unsafe.
• the water content in the ionic type electrolytes, at the time of their preparation, is usually between 500 and 1000 ppm.
• electrolytic solutions have a marked tendency to hydrate both storage and use. This results in a significant loss of efficiency of the electrochemical systems in which these solutions are present. A loss of efficiency in storage is observed after a few months and a loss of efficiency in operation after a few cycles in humid regions, especially in tropical regions.
• electrolytic means any solution used as electrolyte. These include the solutions outlined on page 2 of Allen J.Bard's Electrochemistry Method, and Larry R. Faulkner, 1980 edition of John Wiley & Sons.
• electrolyte is associated with that of an electrochemical generator in which a two-phase electrolyte / electrolyte or electrolyte / electrode system is at the origin of a displacement of charges.
• an electrolyte is essentially defined as a first phase through which a charge is generated by the displacement of ions.
• the electrolytes may be liquid solutions or molten salts, or they may be ionic conductive solids, such as sodium ⁇ -alumina which has mobile sodium ions.
• the second phase at the surface may be another electrolyte, or may be an electrode, which is a phase through which a charge is made by an electronic movement.
• Purifiable electrolytic solutions using the method of the invention preferentially contain: between 0.1 and 2 molar of at least one alkaline earth salt which is preferably selected from the group consisting of KTFSI, NABF 4 , lithium salts and mixtures of at least two of these salts;
• the other impurities being preferably selected from the group consisting of HF, Na and K;
• the process which is the subject of the invention is characterized in that it comprises at least one step of contacting the particles of a calcium salt with the liquid electrolyte to be purified.
• the crosslinking of the polymer is preferably completed in the presence of a crosslinking agent and / or in the presence of a UV source, and after finalization of the purification treatment according to the invention.
• the first group consists of compounds such as alkali halides which are linked mainly by ionic forces and the second group comprises compounds having essentially covalent bonds; this document is incorporated by reference into the present application.
• Melt salts are particular solvents, considered as ionized solvents, in which it is possible to easily dissolve inorganic compounds and work at elevated temperatures. These are often ionic salts such as LiCl-KCl, NaCl-KCl and LiNO 3 -KNO 3 . This definition is extracted from the 2003 session, specific test - PC - National Polytechnic Institute of Toulouse; this document is incorporated by reference into the present application.
• molten salts are salts that are in the liquid state at a temperature between -30 and 350 degrees Celsius, preferably between -20 and 60 degrees Celsius. Indeed, at temperatures above 350 degrees Celsius, the polymers present in the mixtures of the invention could be charred.
• the molten salts of interest in the context of the present invention are those consisting of at least two salts selected from the group consisting of imidazolium, imidinium, pyridinium, ammonium, pyrolium, sulfonium, phosphonium, as well as mixtures of at least two of these.
• the polymer or mixture of polymers, present in the ternary or quaternary mixture, is chosen from the family of polyether-type polymers with 3 branches (preferably those described in the Hydro-Québec patent US-A-6280882), 4 branches (preferably those described in the international patent application of Hydro-Quebec published under the number WO 03/063287), vinyl polymers EG type (preferably those described in the patent application of DKS EP-A- 1249461) and mixtures of at least two of these latter polymers; the documents cited in this paragraph are incorporated by reference into this application.
• the polymers of these preferential families are moreover advantageously chosen from polymers which are crosslinkable by ultraviolet, infrared, heat treatment and / or electron beam (EBeam). These polymers are preferably chosen to be transparent.
• polymers with three branches have the shape of a comb with 3 branches.
• the 3 substantially parallel branches of these polymers are preferably attached to the center and both ends of a small skeleton, preferably having 3 atoms, preferably 2 carbon atoms, in the chain.
• each of these atoms is connected to a branch.
• these polymers with 3 branches and in the context of the present invention, those having a mean molecular weight (MW) ranging from 1000 to 1,000,000 are preferred, more preferably those whose average molecular weight ranges from 5,000 to 100,000.
• Such polymers have the form of a comb with 4 branches.
• the 4 substantially parallel branches of these polymers are respectively fixed between the two ends (preferably symmetrically fixed to the chain) and at the two ends of a small chain preferably consisting of a chain comprising 4 atoms which are preferably 4 carbon atoms.
• each atom is connected to a branch.
• Such polymers preferably have hybrid termini, more preferably hybrid terminations acrylates (preferably methacrylate) and alkoxy (preferably alkoxy with 1 to 8 carbon atoms, more preferably methoxy or ethoxy), or vinyl; at least one branch of said four-branched polymer (and preferably at least two branches) being capable of giving rise to crosslinking.
• hybrid termini more preferably hybrid terminations acrylates (preferably methacrylate) and alkoxy (preferably alkoxy with 1 to 8 carbon atoms, more preferably methoxy or ethoxy), or vinyl; at least one branch of said four-branched polymer (and preferably at least two branches) being capable of giving rise to crosslinking.
• the four-branched polymer is one of those defined in columns 1 and 2 of US-A-6190804 (Ishiko et al.). This document is incorporated by reference in this application.
• Such a polymer is preferably a star polymer of the polyether type which has at least four branches having terminations containing the the following functions: acrylate or methacrylate and alkoxy, allyloxy and / or vinyloxy, of which at least one, and preferably at least two of these functions are active to allow crosslinking.
• the 4-branched polymer is a tetrafunctional polymer preferably of high molecular point corresponding to formula (I):
• R 1 and R 2 each represent a hydrogen atom or a lower alkyl (preferably 1 to 7 carbon atoms);
• R 3 represents a hydrogen atom or a methyl group;
• m and n each represents an integer greater than or equal to 0; in each high molecular point chain, m + n>35; and each of R 1 , R 2 , R 3 and each of the m and n parameters may be the same or different in the 4 high molecular weight chains.
• those having an average molecular weight of between 1,000 and 1,000,000, more preferably still those having an average molecular weight ranging from 5,000 to 100,000 are particularly interesting.
• star-type polyethers of at least four branches with a hybrid termination (acrylate or methacrylate and alkoxy, allyloxy, vinyloxy) are retained.
• the EG-type vinyl polymers and more particularly those described in the patent application of DKS EP-A-1249461 are of particular interest as a protective material. Particularly advantageous among these polymers are those whose average molecular weight ranges from 600 to 2500.
• Polymers of this family may advantageously be obtained by reacting ethylene oxide and propanol-1-epoxy-2,3 with the starting material, or by reacting propanol-1-epoxy-2,3 with ethylene glycol as the starting material for producing a polymer compound. This step is followed by the introduction of polymerizable and / or non-polymerizable functional groups at each end of a backbone and side chains into the resulting polymeric compound.
• Compounds having one or more active hydrogen residues and alkoxide may also be used as starting materials.
• active hydrogen residues for the compound having one or more active hydrogen residues include the group of hydroxyls, preferably having from 1 to 5 active hydrogen residues.
• Specific examples of compounds having one or more active hydrogen residues include triethylene glycol monomethyl ether, ethylene glycol, glycerin, diglycerin, pentaerythritol and their derivatives.
• alkoxide also include CHaONa, t-BuOK and their derivatives.
• the polyetheric polymer compounds of the invention have the unit of structure represented by the formula (1) as well as the unit of structure represented by the formula (2) and / or the unit of structure represented by the formula (3) .
• the number of structural units represented by formula (1) in a molecule is 1 to 22,800, more preferably 5 to 11400, and more preferably
• the number of structural units of formula (2) or (3) (but when both are included is the total number) is 1 to 13,600, more preferably 5 to 6800, and more preferably still from 10 to 3400.
• the formulas (1), (2) and (3) are:
• Examples of polymerizable functional groups introduced at each molecular end include (meth) acrylate residues, allyl groups and vinyl groups, and examples of non-polymerizable functional groups include alkyl groups or functional groups comprising boron atoms.
• alkyl groups having 1 to 6 carbon atoms are preferred, those having 1 to 4 carbon atoms are more preferred, and the methyl groups are of particular interest.
• Examples of functional groups comprising boron atoms include those represented by the following formulas (4) or (5). (4) (5)
• R 11 , and R 12 in formula (4) and R 21 , R 22 , R 23 in formula (5) may be the same or different, and each represents hydrogen, halogen, alkyl, alkoxy, aryl, alkenyl, alkynyl , aralkyl, cycloalkyl, cyano, hydroxyl, formyl, aryloxy, alkylthio, arylthio, acyloxy, sulfonyloxy, amino, alkylamino, arylamino, carbonamino, oxysulfonylamino, sulfonamide, oxycarbonylamino, ureide, acyl, oxycarbonyl, carbamoyl, sulfonyl, sulfinyl, oxysulfonyl, sulfamoyl , carboxylate, sulfonate, phosphonate, heterocyclic, -B (R a ) (R
• (R a ), (R b ) and (R c ) each represent hydrogen, halogen, alkyl, alkoxy, aryl, alkenyl, alkynyl, aralkyl, cycloalkyl, cyano, hydroxyl, formyl, aryloxy, alkylthio, arylthio, acyloxy, sulfonyloxy , amino, alkylamino, arylamino, carbonamino, oxysulfonylamino, sulfonamide, oxycarbonylamino, ureide, acyl, oxycarbonyl, carbamoyl, sulfonyl, sulfinyl, oxysulfonyl, sulfamoyl, carboxylate, sulfonate, phosphonate, heterocyclic or derivatives thereof.
• R 11 , and R 12 in formula (4) and R 21 , R 22 , R 23 in formula (5) may be bonded together to form a ring, and the ring may have substituents. Each group may also be substituted with substitutable groups.
• X + in formula (5) represents an alkali metal ion, and is advantageously a lithium ion.
• the ends of the molecular chains in the polyether polymer may all be polymerizable functional groups, non-polymerizable functional groups, or may include both.
• the average molecular weight (Mw) of this type of polyether polymer compound is not especially limited, but is usually about 500 to 2 million, and preferably about 1000 to 1.5 million.
• the polymers of these preferential families are moreover advantageously chosen from polymers which are crosslinkable by ultraviolet, infrared, heat treatment and / or electron beam (EBeam).
• the formation of the polymer matrix is preferably carried out in the electrochemical system in which the electrolyte precursor is placed, and preferably using one of the methods described in the international patent application published under the number WO 2004/088610 or the application US Hydro-Quebec published under No. 2005/0234177 A1; the contents of these documents are incorporated by reference into the present application.
• the acetylene is removed by evaporation, degassing or purging with inert gases such as nitrogen or helium, which allows to completely eliminate the acetylene formed in the electrolyte solution.
• the size of the CaC 2 particles influences the amount of residual water. It has indeed been highlighted that, through the use micrometrically sized particles and preferably of nanometric size, the contact surface between the water molecules is that developed by the particles of CaC 2 is increased, and thus the amount of residual water removed is at its maximum.
• the mixture is advantageously placed in a mixer operating for a period which is advantageously one hour.
• a centrifuge preferably of ultra-centrifuge type, is used to separate the liquid phase, consisting of the purified electrolyte, the solid phase consisting of calcium hydroxide and a small percentage of calcium carbide. having not reacted.
• a separation of the liquid and solid phases can also be carried out by decantation of the solid phase.
• the process of the invention may be carried out continuously, discontinuously or semi-continuously.
• the calcium carbide recovered by calcining the calcium hydroxide formed during the purification may be advantageously recycled.
• the purification is preferably carried out under an inert atmosphere, more preferably still under argon and / or under nitrogen.
• a first object of the present invention is constituted by a process for purifying an ionic electrolyte containing at least one alkaline earth salt. This method comprises at least one step of contacting the particles of at least one calcium salt preferably selected from the group consisting of CaC 2 , CaH 2 and mixtures of at least two of these with the electrolyte .
• the method of the invention is applied to the purification of a liquid ionic electrolyte, preferably liquid at room temperature, and which contains at least one solvent which ensures the ionic conductivity and which dissolves the alkaline earth salt.
• this solvent being of ionic type.
• the electrolyte is of the gel polymer type, or of the mixture type of at least two gel polymers, and the purification is carried out before the formation of a polymer matrix.
• the ionic electrolyte is of molten salt type (ionic liquid) with or without alkaline earth salt, preferably with or without lithium salt. More preferably still, the electrolyte comprises a molten salt or a mixture of at least two molten salts.
• the ionic electrolyte is a mixture of at least two electrolytes chosen from the group consisting of liquid-type electrolytes, gel and molten salts.
• the purification is applied to a liquid electrolyte which contains:
• a solvent for the alkaline earth salt and which contributes to the ionic conductivity of the solution and - up to 6000 ppm impurities.
• the latter is applied to the purification of a gel electrolyte which contains:
• a polymer or a mixture of polymers preferably up to 30% by weight of a polymer ensuring the formation of a gel matrix within the liquid electrolyte or preferably up to 30% by weight of a polymer mixture providing the formation of one or more gel matrices within the liquid electrolyte.
• the latter is applied to the purification of a molten salt electrolyte which contains: between 0 and 2 molar of at least one alkaline earth salt;
• the anion of the molten salt is bifluoro-sulfonylimide (FSI " ) and / or bi (fluorosulfonyl) imide (TFSI " ).
• the cation of the molten salt is ethyl-3-methylimidazolium (EMI) and / or n-methyl-n-propylpyrolidium and / or n-methylbutylpyrrolidium (PY14 + ) and / or n propyl-piperidinium (PPT3 + ).
• EMI ethyl-3-methylimidazolium
• PY14 + n-methylbutylpyrrolidium
• PPT3 + propyl-piperidinium
• the latter is applied to the purification of an electrolyte mixture chosen from the group of (ionic liquids plus polymer), (ionic liquid plus solvent), and (liquid ionic plus solvent plus polymer).
• the purification process of the invention is applicable to the purification of electrolytes comprising any type of alkaline earth salt but is of particular interest when it is applied to the purification of electrolytes comprising any type of an alkaline earth salt chosen from the group consisting of KTFSI, NABF 4 , lithium salts and mixtures of at least two of these salts.
• the electrolytes which are successfully purified by the process of the invention preferably contain between 50 and 5000 ppm of impurities (including limits), and even more preferably between 700 and 2000 ppm of water (including limits), the other impurities preferably being selected from the group consisting of HF, Na, K and mixtures of at least two of these.
• the latter is implemented using particles of the calcium salt, used to carry out the purification, and which have a d 50 of between 1 and 100 micrometers, terminals included, and more preferably still d 5 o between 10 and 50 micrometers, including terminals.
• the calcium salt particles have a specific surface area, measured according to the BET method, which is between 5 and 200 m 2 / gram, including limits, more preferably still a specific surface area of between 30 and 100 m 2 / grams. , terminals included.
• the amount of calcium salt used is in excess relative to the quantity of water to be removed, this amount preferably representing at least 5 grams per 20 ml of electrolyte to be purified, more preferably still more 10 to 15 grams per 20 ml of electrolyte to be purified.
• the method for purifying the electrolyte of the invention is implemented with the addition of the calcium salt particles in the electrolyte to be purified and by homogenization of the mixture thus obtained, preferably by mechanical stirring and / or ultrasound, preferably for a period of between 5 minutes and 3 hours, preferably also under an inert atmosphere, which is preferably constituted argon, nitrogen or helium or a mixture of these gases, and preferably also at a temperature between 10 and 80 degrees Celsius, more preferably still at a temperature between 25 and 60 degrees Celsius, more preferably still at a temperature of about 40 degrees Celsius.
• the electrolyte is purified by contacting particles of CaC 2 and / or CaH 2 with the electrolyte to be purified.
• the alkaline earth salt is a lithium salt preferably chosen from the group consisting of LiFSI, LiTFSI, LiBETI, LiPF 6 , LiClO 4 , LiBF 4 , UCF 3 SO 3 , LiBOB 1 LiDCTA, and the mixtures of at least two of these, and the lithium salt is present in the electrolyte at a concentration preferably between 0.1 and 2 molar and more preferably between 0.2 and 1 molar expressed relative to the amount of electrolyte.
• the lithium salt may also be present in the electrolyte at a concentration of between 0.5 and 1.5 molar relative to the amount of electrolyte.
• a solvent that dissolves the alkaline earth salt is used, it is preferably a carbonate selected from the group consisting of: EC (ethylene carbide), PC (propylene carbonate), DME (dimethyl ethylene), DMC (dimethyl carbonate) ), DEC (diethylcarbonate), EMC (ethylmethylcarbonate), GBL (gamabutyrolactone) and mixtures of at least two of these, the solvent being the reference molar to which the amount of alkaline earth salt to be added is calculated.
• EC ethylene carbide
• PC propylene carbonate
• DME dimethyl ethylene
• DMC dimethyl carbonate
• DEC diethylcarbonate
• EMC ethylmethylcarbonate
• GBL gamabutyrolactone
• the polymer is of the polyether type; siloxane, PVDF (polyvinyl difluoro), polyacrylonitrile, EPDM (ethylene propylenediethyl monomer), PMMA (polymethyl methacrylate) or a blend of at least two of these polymers; the polymer content in the electrolyte is preferably between 1 and 30%, more preferably between 5 and 15% of the total weight of the electrolyte.
• step a) mixing the electrolyte with an amount of a calcium salt which corresponds to an excess of the quantity of water to be removed, preferably of mechanical mixing carried out in a mixer and for a duration of between 5 minutes and 3 hours, more preferably for a period of about 1 hour, and preferably with elimination of the gases formed; b) separation by decantation, centrifugation, or by ultracentrifugation or by a combination of at least two of these techniques, of the solid phase, consisting in particular of the calcium hydroxide formed in step a) and of the excess calcium salt, the liquid phase consisting of the purified electrolyte; and c) optionally converting the calcium hydroxide to calcium carbide, preferably by calcination, and recycling the calcium carbide thus obtained in step a), removing the solid phase from the mixture obtained at the end of step a) to be finalized rapidly, preferably in less than 10 minutes and even more preferably in less than 5 minutes after the end of step a), and steps a) and b) can be
• alkaline earth salt between 0.1 and 2 molar of an alkaline earth salt, the amount of alkaline earth salt being expressed relative to the amount of molten salt; and - with or without a solvent;
• step a) mixing the electrolyte with an amount of a calcium salt which corresponds to an excess of the quantity of water to be removed, preferably of mechanical mixing carried out in a mixer and for a duration of between 5 minutes and 3 hours, more preferably for a period of about 1 hour, and preferably with removal of the mixture of the gases formed; b) separation by decantation, centrifugation, or by ultracentrifugation or by a mixture of at least two of these techniques, of the solid phase, consisting in particular of the calcium hydroxide formed in step a) and of the excess calcium salt, the liquid phase consisting of the purified electrolyte; and c) optionally converting the calcium hydroxide to calcium carbide, preferably by calcination, and recycling the calcium carbide thus obtained in step a), the step of removing the solid phase from the mixture obtained in the end of step a) to be finalized rapidly, preferably in less than 10 minutes and even more preferably in less than 5 minutes after the end of step a), and steps a)
• Another preferred mode of implementation of the invention is the application to the purification of a gel type electrolyte.
• the purification is carried out from an electrolyte precursor containing:
• a solvent between 50 and 5000 ppm of impurities, preferably 700 to 2000 ppm of water; and
• step d) optionally converting the calcium hydroxide to calcium carbide, preferably by calcination, and recycling the calcium carbide thus obtained in step a), removing the solid phase from the mixture obtained at the end of step a) to be finalized rapidly, preferably in less than 10 minutes and even more preferably in less than 5 minutes after the end of step a), and steps a) and b) can be carried out as often than necessary to achieve the desired degree of purification.
• the purification process of the invention independently of the electrolyte to be purified, can be carried out continuously, and in this case preferably
• step c) the calcium carbide recovered in step c) is recycled in step a);
• the purification is preferably carried out under an inert atmosphere, more preferably still under argon and / or under nitrogen.
• the purification process of the invention independently of the electrolyte to be purified, can be carried out semi-continuously, and in this case preferably by percolating the liquid electrolyte on a bed of calcium salt continuously until the calcium salt bed is exhausted.
• a second object of the present invention is constituted by a purified liquid electrolyte obtained by implementing one of the methods according to the first subject of the present invention.
• this electrolyte contains less than 20 ppm of one or more impurities. More preferably, the electrolyte contains less than 1 ppm of one or more impurities. This impurity is advantageously water.
• the liquid electrolyte comprises:
• At least one alkaline earth salt at least one alkaline earth salt
• electrolyte satisfying at least one of the following conditions:
• the liquid electrolyte will comprise: less than 5 ppm in water;
• liquid electrolyte will comprise:
• liquid electrolyte will comprise:
• a third object of the present invention is constituted by an electrochemical generator comprising a purified electrolyte obtained by implementing a method constituting the first subject of the present invention, or comprising one of the purified electrolytes constituting the second subject of the present invention.
• the generator is advantageously of the Li-ion type or of the Li-metal type.
• the anode is graphite, carbon, carbon fiber, alloy, Li 4 Ti 5 O 2 or a mixture of at least two of these last.
• the cathode is chosen from the group consisting of cathodes of LiCoO 2 , LiMnN 2 O 4 , LiFeMPO 4 , LiFePO 4 , LiCo 1 Z 3 MnIz type. 3 Ni 1 Z 3 , LiCoPO 4 , Li 4 Ti 5 O 12 or a mixture of at least two of these.
• a fourth subject of the present invention is constituted by a process for purifying an impure alacalino-earth salt, said process consisting in solubilizing the alkaline-earth salt in a solvent at a low evaporation temperature, preferably chosen from the group consisting of with acetone, toluene, heptane, ethanol and mixtures of at least two of these, and with very low water content, and then treating the alkaline earth salt solution thus obtained with an excess of calcium salt, and finally separating the liquid phase containing the alkaline earth salt and the solvent from the solid phase containing impurities and sodium hydroxide.
• the impure alkaline earth salt is selected from lithium, sodium, potassium and impure mixtures of at least two of these.
• impure lithium salts will be chosen.
• this purification process is applied to an alkaline earth salt, preferably to a lithium salt which is selected from the group consisting of LiFSI, LiTFSI, LiBETI, LiPF 6 , LiClO 4 , LiBF 4 , LiCl 3 SO 3. , LiBOB, LiDCTA and mixtures of at least two of these.
• a lithium salt which is selected from the group consisting of LiFSI, LiTFSI, LiBETI, LiPF 6 , LiClO 4 , LiBF 4 , LiCl 3 SO 3. , LiBOB, LiDCTA and mixtures of at least two of these.
• the alkaline earth salts, preferably the lithium salts, to be purified have levels of impurities, preferably water or HF or a mixture thereof, of between 100 and 500 ppm.
• the alkaline earth salts to be purified are chosen from the group of impure salts of calcium, potassium, lithium and mixtures of at least two of these.
• the lithium salts to be purified are chosen from the group consisting of LiFSI, LiTFSI, LiBETI, LiPF 6 and mixtures of at least two of these. Particularly advantageous performances are obtained when the purification is carried out with a ratio of lithium salt to be purified / solvent at a low evaporation temperature, which is between 0.1 M and 2 M, preferably between 0.2 M and 0.2 M. and 1 M.
• a fifth object of the present invention is constituted by the alkaline earth salts, preferably by the purified lithium salts, obtained by carrying out one of the methods constituting the fourth subject of the present invention.
• these purified alkaline earth salt are characterized by at least one of the following characteristics.
• Example 1 The lithium salts used in Examples 4 and 5 are commercial products.
• Example 1 The lithium salts used in Examples 4 and 5 are commercial products.
• the impurities identified in the electrolyte are HF and H 2 O at contents of 200 and 1100 ppm, respectively.
• the preparation is carried out in a glove box under helium atmosphere. Then, the bottle is placed, for 1 hour, in a mixer located outside the glove box. Then, the bottle of the mixture is placed in an ultra-centrifuge operated at a rotation speed of 13000 rpm (rpm) for 5 minutes, in order to separate the liquid phase from the solid phase.
• the purified electrolyte is decanted into the glove box.
• the treatment is repeated 3 times in order to eliminate the maximum of traces of solids and impurities.
• the amount of residual water in the purified final electrolyte, measured by the Karl Fisher method, is less than 1 ppm.
• LiFSI LiFSI
• the impurities identified in the electrolyte are HF and H 2 O.
• the content of H 2 O is 1000 ppm and that of HF 150 ppm.
• the color of the solution is yellowish.
• Two identical button cells are mounted with 0.2 ml of the unpurified 1M LiFSI + EC + ⁇ BL solution, and according to the following arrangement:
• Electrochemistry shows that the capacity obtained after cycling in C / 24 (the charge in 24 hours and the discharge in 24 hours) is 5.25 mAh / g of LiFePO 4 , which is equivalent to 3% of the theoretical capacity. .
• the 1M LiFSI solution in EC + ⁇ BL previously used is purified according to the method of the invention, carried out under the same conditions as in Example 1 above. It is found that its water content is reduced to 1 ppm and that the color of the solution is clear.
• the two button cells of NG / 1M type LiFSI EC + ⁇ BL (purified) / LiFePO 4 mounted with 0.5 ml of the purified solution have an impedance of 9 Ohms.
• the impurities identified in the electrolyte are HF and H2O.
• the content of H 2 O is 1400 ppm.
• the capacity of the two button cells is 3.5 mAh / g of LiFePO 4 , which corresponds to 2% of the theoretical capacity.
• the 1M LiDCTA + EC + ⁇ BL solution is purified according to the method of the invention, carried out under the conditions of Example 1, until a water content of 2 ppm is obtained. The solution obtained is clear.
• the commercial electrolytic solution has a water content of 20 ppm, 14 ppm HF, and 1 ppm in each of Ca, Fe and K species.
• the impedance of both button cells is increased to 770 ohms.
• the capacity obtained is 4% of the theoretical capacity.
• the 1M LiPF 6 + EC + DEC solution containing 1000 ppm of water is purified according to the method of the invention, carried out under the conditions of Example 1, until a water content of 1 ppm is obtained and HF 3 ppm.
• the impedance of these two batteries is 7 Ohms and the capacity is 80% of the theoretical capacity.
• Example 5 storage of the electrolyte:
• the 1M LiPF 6 + EC + DEC solution marketed by the company Tomiyama in 2003 is used for the realization of the example. This solution initially contains 20 ppm of water and 14 ppm of HF. It is stored outside the glove box for 11 months.
• Two button cells are mounted as follows:
• the impedance of the two cells is 450 Ohms.
• the capacity obtained is 8.7 mAh / g of LiFePO 4 , which gives 5% of the theoretical capacity.
• the solution is purified according to the method of the invention implemented under the conditions of Example 1.
• the water content is 1 ppm, and that of HF 3 ppm.
• the impedance of the two button cells, mounted with the purified solution, is 7 Ohms.
• the capacity of these batteries is 140 mAh / g of LiFePo 4 , which corresponds to 80% of the theoretical capacity.
• the water content measured in the purified electrolyte is 1200 ppm.
• the preparation is carried out in a glove box under helium atmosphere.
• the bottle is placed, for 1 hour, in a mixer located outside the glove box.
• the bottle of the mixture is placed in an ultra-centrifuge operated at a rotation speed of 13000 rpm for 5 minutes, in order to separate the liquid and solid phases.
• the purified electrolyte is decanted into the glove box.
• the treatment is repeated three times in order to eliminate the maximum of traces of solids and impurities.
• the amount of residual water in the purified final electrolyte, measured by the Karl Fisher method, is less than 5 ppm water.
• CACA calcium carbide
• EMI + ethyl-methyl-imidazolium
• TFSI bis-trifluoromethanesulfonyl imide
• the water content measured in the purified electrolyte is 1100 ppm.
• the preparation is carried out in a glove box under helium atmosphere. Then, the bottle is placed, for 1 hour, in a mixer located outside the glove box. Then, the bottle of the mixture is placed in an ultra-centrifuge operated at a rotation speed of
• the purified electrolyte is decanted into the glove box.
• the treatment is repeated three times in order to eliminate the maximum of traces of solids and impurities.
• the amount of residual water in the purified final electrolyte measured by the Karl Fisher method, is less than 7 ppm water.
• the preparation is carried out in a glove box under helium atmosphere. Then, the bottle is placed, for 1 hour, in a mixer located outside the glove box. Then, the bottle of the mixture is placed in an ultra-centrifuge operated at a rotation speed of 13000 rpm for 5 minutes, in order to separate the liquid and solid phases.
• the purified electrolyte is decanted into the glove box.
• the treatment is repeated three times in order to eliminate the maximum of traces of solids and impurities.
• the quantity of residual water in the purified final electrolyte, measured by the Karl Fisher method, is less than 10 ppm of water
• the water content measured in the purified electrolyte is 1300 ppm.
• the preparation is carried out in a glove box under helium atmosphere. Then, the bottle is placed, for 1 hour, in a mixer located outside the glove box. Then, the bottle of the mixture is placed in an ultra-centrifuge operated at a rotation speed of 13000 rpm for 5 minutes, in order to separate the liquid and solid phases.
• the purified electrolyte is decanted into the glove box.
• the treatment is repeated three times in order to eliminate the maximum of traces of solids and impurities.
• the amount of residual water in the purified final electrolyte measured by the Karl Fisher method, is less than 10 ppm water.
• the measured H 2 O content in the purified electrolyte is 2000 ppm.
• the preparation is carried out in a glove box under helium atmosphere. Then, the bottle is placed, for 1 hour, in a mixer located outside the glove box. Then, the bottle of the mixture is placed in an ultra-centrifuge operated at a rotation speed of 13000 rpm for 5 minutes, in order to separate the liquid and solid phases.
• the purified electrolyte is decanted into the glove box.
• the treatment is repeated three times in order to eliminate the maximum of traces of solids and impurities.
• the amount of residual water in the purified final electrolyte measured by the Karl Fisher method, is less than 10 ppm water.
• One of the particularly interesting applications of the invention lies in the possibility of purifying electrolytes stored for more than six months.
• This purification technique is particularly economical for battery companies, as well as for those that produce electrolytes. Indeed, in the case of battery production companies, any production problem that lasts several weeks could cause the loss of the entire electrolyte stock.
• the electrolyte producing companies may use the purification method as a final step after the electrolyte synthesis. In fact, the residual water will be removed and thus the storage time of the electrolyte is prolonged.
• lithium salt producers can improve the quality of lithium salts which are often obtained in an impure and optionally hydrated solid form.
• Lithium salts are known by their hygroscopic properties.
• the solubilization of the lithium salt is first carried out in a solvent with a low evaporation temperature, such as acetone, toluene, heptane, ethanol or a mixture of at least two of these, and at very low water content.
• Treatment of the lithium salt solution with an excess of calcium salt (excess relative to the amount of water present in the solution) makes it possible to reduce the water content to a scale of a few ppm after separation of the liquid phases. and solid.
• the method of the invention provides new electrolytes characterized by an exceptional degree of purity and thus opens the door to the preparation of electrochemical systems using an electrolyte based on a lithium salt and a level of performance never reached so far.

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• 2005
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• 2006
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