Novel materials for use as electrolytic solutes

Abstract

The invention relates to ionic compositions having a high ionic conductivity comprising a salt with a delocalized anionic charge. An ionic composition comprises a salt in solution in a solvent and has a conductivity of greater than 10 −5 S.cm −1 between −30° C. and 150° C. The cation is a proton, a hydronium, a hydroxonium, a nitrosonium NO + , an ammonium NH 4 + or a metal, organic or organometallic cation. The anion is a carbanion carrying a perfluorinated substituent or a substituent carrying at least one F on the carbon α to the carbanion and two nonperfluorinated electron-withdrawing substituents. Use as electrolyte in electrochemical devices, as catalyst of chemical reactions, or as photochemical or thermochemical initiator for polymerization or crosslinking reactions.

1 . Ionic composition comprising at least one ionic compound in solution in a solvent, the said compound comprising an anionic part associated with at least one cationic part M m+  in a number sufficient to ensure the electronic neutrality of the combination, the said composition being characterized in that it has a conductivity of greater than 10 −5  S.cm −1  at a temperature of between −30° C. and 150° C., in that M m+  is a proton, a hydronium, a hydroxonium, a nitrosonium NO + , an ammonium —NH 4   +  or a cation having the valency m chosen from metal cations, organic cations and organometallic cations, and in that the anionic part corresponds to one of the formulae X F —SO x C − (Z) (Z′), X F —SO x —C − (YR) (Y′R′) or X F —SO x —C − (Z) (YR) in which: 
 x is 1 or 2;  
 X F  represents a monovalent or multivalent radical chosen from the group consisting of linear, branched or cyclic perhalogenated radicals of the alkyl, alkylaryl, oxa-alkyl, aza-alkyl, thia-alkyl, alkenyl, oxa-alkenyl, aza-alkenyl, thia-alkenyl or dialkylazo type or from the group consisting of organic radicals in which the carbon α to the SO x  group carries at least one F atom, it being understood that a multivalent X F  radical is connected to more than one —SO x C— group;  
 Z and Z′ represent, independently of one another, a monovalent or multivalent electron-withdrawing radical, it being understood that a multivalent Z or Z′ radical can be connected to several —C − SO x —X F  groups;  
 Y or Y′ represent a sulfonyl, sulfinyl, carbonyl or phosphonyl group;  
 R is a monovalent or multivalent organic radical and R′ is H or a monovalent or multivalent organic radical, R and R′ being other than a perfluoroalkyl when x=2;  
 it being understood that each of the substituents R, R′, Z or Z′ can form part of an aromatic or nonaromatic ring or of a polymer and that each of the substituents X F , R, R′, Z or Z′ can be connected to a substituent X F , R, R′, Z or Z′ carried by the same anionic center C −  or by another anionic center.  
 
     
     
         2 . Ionic composition according to  claim 1 , characterized in that the cation of the ionic compound is a metal cation chosen from alkali metal cations, alkaline earth metal cations, transition metal cations in the divalent or trivalent state, and rare earth cations.  
     
     
         3 . Ionic composition according to  claim 1 , characterized in that the cation of the ionic compound is an organometallic cation or a cation of a transition metal complexed by ligands of phosphine type, the said cation optionally forming part of a polymer chain.  
     
     
         4 . Ionic composition according to  claim 1 , characterized in that the cation of the ionic compound is an organic cation chosen from the group consisting of the R″ 3 O + (onium), NR″ 4   + (ammonium), R″C(NHR″ 2 ) 2   + (amidinium), C(NHR″ 2 ) 3   + (guanidinium), C 5 R″ 6 N + (pyridinium), C 3 R″ 5 N 2   + (imidazolium), C 2 R″ 4 N 3   + (triazolium), C 3 R″ 7 N 2   + (imidazolinium), SR″ 3   + (sulfonium), PR″ 4   + (phosphonium), IR″ 2   + (iodonium) or (C 6 R″ 5 ) 3 C + (carbonium) cations, the R″ radicals independently representing H or a nonperfluorinated organic radical.  
     
     
         5 . Ionic composition according to  claim 4 , characterized in that the R″ radicals, which are identical or different, are chosen from the group consisting of: 
 the proton, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, optionally hydrolyzable sila-alkyl or optionally hydrolyzable sila-alkenyl radicals and dialkylazo radicals, it being possible for the said radicals to be linear, branched or cyclic;  
 cyclic or heterocyclic radicals optionally comprising at least one side chain comprising heteroatoms, such as nitrogen, oxygen or sulfur;  
 aryls, arylalkyls, alkylaryls and alkenylaryls, optionally comprising heteroatoms in the aromatic nucleus or in a substituent;  
 groups comprising several condensed or noncondensed, aromatic or heterocyclic nuclei, optionally comprising at least one nitrogen, oxygen, sulfur or phosphorus atom.  
 
     
     
         6 . Ionic composition according to  claim 4 , characterized in that the cation carries at least two R″ radicals other than H, these radicals optionally together forming an aromatic or nonaromatic ring encompassing or not encompassing the center carrying the cationic charge.  
     
     
         7 . Ionic composition according to  claim 4 , characterized in that the cationic group is polycationic.  
     
     
         8 . Ionic composition according to  claim 4 , characterized in that the cation is a cationic heterocycle of aromatic nature comprising at least one quaternized nitrogen atom in the ring.  
     
     
         9 . Ionic composition according to  claim 8 , characterized in that the cation is chosen from the group consisting of imidazolium, triazolium, pyridinium and 4-(dimethylamino)pyridinium and of the said cations optionally carrying a substituent on the carbon atoms of the ring.  
     
     
         10 . Ionic composition according to  claim 4 , characterized in that the cation possesses an —N═N— or —N═N + linkage, a sulfonium group, an iodonium group or an areneferrocenium cation which is substituted or unsubstituted, optionally incorporated in a polymeric backbone.  
     
     
         11 . Ionic composition according to  claim 4 , characterized in that the cation comprises a 2,2′[Azobis(2-2′-imidazolinio-2-yl)propane] 2+ or 2,2′-Azobis(2-amidiniopropane) 2+ group.  
     
     
         12 . Ionic composition according to  claim 1 , characterized in that X F  is a perhalogenated alkyl radical having from 1 to 12 carbon atoms or a perhalogenated alkylaryl radical having from 6 to 9 carbon atoms, it being possible for the said radicals to comprise an O, N or S heteroatom between two carbon atoms or at the end of the radical.  
     
     
         13 . Ionic composition according to  claim 1 , characterized in that X F  is chosen from the group consisting of R H CF 2 —, R H CF 2 CF 2 —, R H CF 2 CF(CF 3 )— and CF 3 C(R H ) F—, R H  representing a nonperhalogenated organic radical.  
     
     
         14 . Ionic composition according to either of claims  1  and  13 , characterized in that R, R′ or R H  are chosen, independently of one another, from the group consisting of alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl and dialkylazo radicals having from 1 to 24 carbon atoms or of aryl, arylalkyl, alkylaryl and alkenylaryl radicals having from 5 to 24 carbon atoms, it being possible for the said radicals optionally to be completely or partially fluorinated, R and R′ being other than a perfluorosalkyl when X F SO x  is a perfluoroalkylsufonyl.  
     
     
         15 . Ionic composition according to  claim 1 , characterized in that two R and R′ substituents together form a divalent radical connected to a Y group and a Y′ group.  
     
     
         16 . Ionic composition according to either of claims  1  and  13 , characterized in that R, R′ or R H  represent, independently of one another, an alkyl radical having from 1 to 12 carbon atoms or an alkenyl radical having from 2 to 12 carbon atoms and optionally comprising at least one O, N or S heteroatom in the main chain or in a side chain and/or optionally carrying a hydroxyl group, a carbonyl group, an amine group, an alkoxysilane group or a carboxyl group.  
     
     
         17 . Ionic composition according to either of claims  1  and  13 , characterized in that R and R′ together form a biradical connected, at each of its ends, to an —SO 2 —C − SO 2 X F  anionic group.  
     
     
         18 . Ionic composition according to either of claims  1  and  13 , characterized in that an R, R′ or R H  substituent is a polymer radical.  
     
     
         19 . Composition according to  claim 1 , characterized in that an R or R′ substituent is a repeat unit of a polymer.  
     
     
         20 . Composition according to either of  claim 1  and  13 , characterized in that an R, R′ or R H  substituent possesses at least one anionic ionophoric group and/or at least one cationic ionophoric group.  
     
     
         21 . Composition according to either of  claim 1  and  13 , characterized in that an R, R′ or R H  substituent comprises at least one ethylenic unsaturated and/or one condensable group and/or one group dissociable by the thermal route, by the photochemical route or by ionic dissociation.  
     
     
         22 . Composition according to either of  claim 1  and  13 , characterized in that an R, R′ or R H  substituent comprises a mesomorphic group, a chromophoric group, a self-doped electronic conducting polymer or a hydrolyzable alkoxysilane.  
     
     
         23 . Composition according to either of  claim 1  and  13 , characterized in that an R, R′ or R H  substituent comprises a group capable of scavenging free radicals, a dissociating dipole, a redox couple, a complexing ligand, an optically active group, or an optically or biologically active polypeptide.  
     
     
         24 . Ionic composition according to  claim 1 , characterized in that Z or Z′ is chosen from the group consisting of —CN, —NO 2 , —SCN, —N 3 , —CF 3 , R′ F CH 2 —(R′ F  being a perfluorinated radical), CF 2 ═CFO—, CF 2 ═CF—S—, CF 2 ═CF—, —C 2 F 4 H, fluoroalkyloxy radicals, perfluoroalkyloxy radicals, fluoroalkylthioxy radicals and perfluoroalkylthioxy radicals.  
     
     
         25 . Ionic composition according to  claim 1 , characterized in that Z or Z′ is a radical comprising one or more aromatic nuclei optionally comprising at least one nitrogen, oxygen, sulfur or phosphorus atom, it being possible for the said nuclei optionally to be condensed nuclei and/or it being possible for the said nuclei optionally to carry at least one substituent chosen from the group consisting of halogens, —OC n F 2n+1 , —OC 2 F 4 H, —SC n F 2n+1 , —SC 2 F 4 H, —O—CF═CF 2 , —SCF═CF 2 , —CN, —NO 2 , —SCN, —N 3 , —CF 3 , CF 3 CH 2 —, aza, thia and oxa radicals, perfluoroalkyl radicals, fluoroalkyloxy radicals, fluoroalkylthioxy radicals, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl radicals, polymer radicals, and radicals possessing at least one cationic ionophoric group and/or at least one anionic ionophoric group; 
 it being understood that a Z or Z′ substituent can be a monovalent radical, a portion of a multivalent radical connected to several X F —SO x —C −  groups, or a segment of a polymer, and that two Z and Z′ substituents can together form a multivalent group comprising a nucleus or several optionally condensed aromatic nuclei, including or not including the carbon carrying the anionic charge.  
 
     
     
         26 . Ionic composition according to  claim 1 , characterized in that Z or Z′ is a repeat unit of a polymer.  
     
     
         27 . Ionic composition according to  claim 1 , characterized in that the solvent of the ionic composition is an aprotic liquid solvent, a polar polymer or one of their mixtures.  
     
     
         28 . Ionic composition according to  claim 27 , characterized in that the aprotic liquid solvent is chosen from linear ethers and cyclic ethers, esters, nitrites, nitro derivatives, amides, sulfones, sulfolanes, alkylsulfamides and partially halogenated hydrocarbons.  
     
     
         29 . Ionic composition according to  claim 27 , characterized in that the solvent is a crosslinked or noncrosslinked solvating polymer carrying or not carrying grafted ionic groups.  
     
     
         30 . Ionic composition according to  claim 27 , characterized in that the solvent is a solvating polymer chosen from 
 polyethers with a linear, comb or block structure, forming or not forming a network, based on poly(ethylene oxide),    copolymers comprising the ethylene oxide or propylene oxide or allyl glycidyl ether unit,    polyphosphazenes,    crosslinked networks based on poly(ethylene glycol) crosslinked by isocyanates or networks obtained by polycondensation and carrying groups which make possible the incorporation of crosslinkable groups, and    block copolymers in which some blocks carry functional groups which have redox properties.    
     
     
         31 . Ionic composition according to  claim 27 , characterized in that the solvent comprises an aprotic liquid and a polar polymer comprising units comprising at least one heteroatom chosen from sulfur, nitrogen, oxygen and fluorine.  
     
     
         32 . Ionic composition according to  claim 1 , characterized in that it comprises a second salt.  
     
     
         33 . Ionic composition according to  claim 1 , characterized in that it comprises an inorganic or organic filler in the form of a powder or of fibers.  
     
     
         34 . Electrochemical device, characterized in that it comprises, as electrolyte, an ionic composition according to one of  claims 1  to  33 .  
     
     
         35 . Electrochemical generator comprising a negative electrode and a positive electrode separated by an electrolyte, characterized in that the electrolyte is an ionic composition according to one of  claims 1  to  33 .  
     
     
         36 . Generator according to  claim 35 , characterized in that the negative electrode is composed of metallic lithium or of one of its alloys, optionally in the form of a nanometric dispersion in lithium oxide, or of a double lithium and transition metal nitride, or of an oxide of low potential having the general formula Li 1+y+x/3 Ti 2-x/3 O 4  (0≦×≦1, 0≦y≦1), or of carbon and carbonaceous products resulting from the pyrolysis of organic matter.  
     
     
         37 . Generator according to  claim 35 , characterized in that the active material of the positive electrode is chosen from vanadium oxides VO x  (2≦×≦2.5), LiV 3 O 8 , Li y Ni 1-x Co x O 2 , (0≦×≦1; 0≦y≦1), manganese spinels Li y Mn 1-x M x O 2  (M=Cr, Al, V, Ni, 0≦×≦0.5; 0≦y≦2), organic polydisulfides, FeS, FeS 2 , iron sulfate Fe 2 (SO 4 ) 3 , iron and lithium phosphates and phosphosilicates of olivine structure, or their products of substitution of the iron by manganese, used alone or as mixtures.  
     
     
         38 . Generator according to  claim 35 , characterized in that the collector of the positive electrode is made of aluminum.  
     
     
         39 . Generator according to  claim 35 , characterized in that the ionic compound of the electrolyte is an alkali metal salt.  
     
     
         40 . Generator according to  claim 35 , characterized in that the R and R′ substituents of the ionic compound of the electrolyte represent an alkyl, an aryl, an alkylaryl or an aralkyl having from 6 to 20 carbon atoms.  
     
     
         41 . Generator according to  claim 35 , characterized in that at least one R, R′ or X F  substituent of the ionic compound of the electrolyte comprises a mesomorphic group or an ethylenic unsaturation and/or a condensable group and/or a group dissociable by the thermal route, by the photochemical route or by ionic dissociation.  
     
     
         42 . Generator according to  claim 35 , characterized in that the salt of the electrolyte carries at least one R, R′ or R H  substituent which is a self-doped electronic conducting polymer.  
     
     
         43 . Generator according to  claim 35 , characterized in that the salt of the electrolyte carries an R, R′ or R H  substituent which comprises a redox couple.  
     
     
         44 . Generator according to  claim 35 , characterized in that the solvent comprises a polar aprotic liquid solvent.  
     
     
         45 . Generator according to  claim 35 , characterized in that the solvent comprises a solvating polar polymer.  
     
     
         46 . Generator according to  claim 35 , characterized in that the cathode is composed of a composition according to  claim 1  in which the ionic compound is an electronic conducting polymer.  
     
     
         47 . Supercapacitor comprising an electrolyte and at least one carbon electrode with a high specific surface or one electrode comprising a redox polymer, characterized in that the electrolyte is an ionic composition according to  claim 1 .  
     
     
         48 . Supercapacitor according to  claim 47 , characterized in that the cation of the electrolyte is an ammonium NH 4   + , a metal cation or an organic cation comprising a quaternized nitrogen atom.  
     
     
         49 . Supercapacitor according to  claim 47 , characterized in that the electrolyte comprises a salt in which R, R′ and X F  have an atom number of less than 3 and optionally a second salt in which R and/or R′ are are alkyl chains having at least 8 carbon atoms.  
     
     
         50 . Supercapacitor according to  claim 47 , characterized in that the solvent of the electrolyte is chosen from acetonitrile, alkyl carbonates or the ethylene carbonate and dimethoxyethane mixture.  
     
     
         51 . Fuel cell, characterized in that it comprises, as electrolyte, an ionic composition according to  claim 1 .  
     
     
         52 . Fuel cell according to  claim 51 , characterized in that the salt of the electrolyte has an XF—SO x —C − —(Z) (Z′) or X F —SO x —C − (Z) (YR) anion and a cation chosen from hydronium, ammonium, metal cations and organic cations comprising a quaternized nitrogen atom (as partial replacement for hydronium).  
     
     
         53 . Fuel cell according to  claim 52 , characterized in that Z and Z′ represent, independently of one another, —ΦOC n F 2n+1 , —ΦOC 2 F 4 H, —ΦSC n F 2n+1 , —ΦSC 2 F 4 H, —ΦOCF═CF 2 , —ΦSCF═CF 2 , —C 2 F 4 H, or CF 2 ═CF—, n being an integer from 1 to 8.  
     
     
         54 . Electrophotochemical device having, as electrolyte, an ionic composition according to  claim 1 .  
     
     
         55 . Electrophotochemical device according to  claim 54 , characterized in that the salt of the ionic composition is a salt of a cation chosen from the group consisting of H + , H 3 O + , Na + , K + , NH 4   + , imidazolium, triazolium, pyridinium or 4-(dimethylamino)pyridinium.  
     
     
         56 . Electrophotochemical device according to  claim 54 , characterized in that the salt of the electrolyte carries at least one R, R′ or R H  substituent comprising a redox couple.  
     
     
         57 . Electrophotochemical device according to  claim 54 , characterized in that the salt of the electrolyte has molten salt properties.  
     
     
         58 . Device for optical display, characterized in that it comprises, as electrolyte, a composition according to  claim 1 .  
     
     
         59 . Device for optical display according to  claim 58 , characterized in that the salt of the electrolyte carries at least one R, R′ or R H  substituent chosen from alkyl, aryl, alkylaryl or a arylalkyl radicals having from 6 to 20 carbon atoms.  
     
     
         60 . Process for the polymerization or for the crosslinking of monomers or of prepolymers capable of reacting by the cationic route, characterized in that use is made of an ionic composition of the invention as photoinitiator source of acid catalyzing the polymerization reaction.  
     
     
         61 . Process according to  claim 60 , characterized in that the cation of the salt of the ionic composition is a proton, an oxonium, Li, Mg, Cu, a rare earth [lacuna], trimethylsilyl, a ferrocene, a zirconocene or a zirconoindocene.  
     
     
         62 . Process according to  claim 60 , characterized in that the cation of the salt is a group possessing an —N═N + or —N═N— linkage, a sulfonium group, an iodonium group or an areneferrocenium cation which is substituted or unsubstituted, optionally incorporated in a polymeric backbone.  
     
     
         63 . Process according to  claim 60 , characterized in that it consists in mixing at least one monomer or prepolymer capable of polymerizing by the cationic route and at least one ionic composition of the invention and in subjecting the mixture obtained to actinic radiation or radiation.  
     
     
         64 . Use of a composition according to  claim 1 , in which the cation of the ionic compound is chosen from the group consisting of H, lithium, magnesium, transition metals in the divalent or trivalent state, rare earths, platinoids and their organometallic couples, as catalyst in Friedel-Craft reactions, Diels-Alder reactions, aldol reactions, Michael additions, allylation reactions, pinacol coupling reactions, glycosilation reactions, ring opening reactions of oxetanes, methathesis reactions of alkenes, polymerizations of Ziegler-Natta type, polymerizations of the methathesis type by ring opening and polymerizations of the methathesis type of acyclic dienes.  
     
     
         65 . Use of a composition according to  claim 1 , in which the cation of the salt is chosen from the group consisting of imidazolium, triazolium, pyridinium and 4-(dimethylamino)pyridinium, the said cation optionally carrying a substituent on the carbon atoms of the ring, and the anion of the salt carries substituents which have a number of carbon atoms of less than or equal to 4, as solvent for chemical, photochemical, electrochemical or photoelectrochemical reactions.  
     
     
         66 . Dye composition, characterized in that it comprises an ionic composition according to  claim 1  comprising a salt wherein the negative charge or charges of the X F —SO x —C − (Z) (Z′), X F SO x —C − (YR) (Y′R′) or X F —SO x —C − (Z) (YR) anionic group are either attached to a dye molecule or constitute the counterion of the positive charges of the dye.