Solvents and novel electrolytic compositions having a large range of stability and high conductivity

Abstract

The present invention is concerned with novel polar solvents and novel electrolytic compositions comprising such solvents, and having a high range of stability, as required for applications in the field of electrochemistry. The present solvents have a highly polar amide function, and preferably combine with a salt soluble in the solvent and having an anion with a delocalized charge, and at least one polymer, to form an electrolytic composition.

1 . An aprotic polar compound having solvent properties and having the formula:
   R 1 R 2 NX(Z)R 7      wherein   X═C or SO;   Z=O, NSO 2 NR 3 R 4  or NCN;   R 1  and R 2  are the same or different and are C 1-18  alkyl, C 1-18  oxaalkyl, C 1-18  alkylene, C 1-18  oxaalkylene;   R 7  is R F , R F CH 2 O—, (R F ) 2 CHO—, or (R F CH 2 ) 2 N— or R 5 R 6 N—;   R 3  to R 6  are the same or different and are C 1-18  alkyl or C 1-18  oxaalkyl;   R F  is C 1-4  alkyl, C 1-4  oxaalkyl, C 1-4  azaalkyl, wherein C 1-4  alkyl, C 1-4  oxaalkyl, C 1-4  azaalkyl are each perfluorinated,   with the proviso that if Z=O then R 7  is not NR 5 R 6 .   
   
   
       2 . An electrolytic composition, comprising:
 at least one aprotic polar compound having solvent properties and having the formula:
   R 1 R 2 NX(Z)R 7    
   wherein   X═C or SO;   Z=O, NSO 2 NR 3 R 4  or NCN;   R 1  and R 2  are the same or different and are C 1-18  alkyl, C 1-18  oxaalkyl, C 1-18  alkylene, C 1-18  oxaalkylene;   R 7  is R F , R F CH 2 O—, (R F ) 2 CHO—, or (RFCH 2 ) 2 N— or NR 5 R 6 ;   R 3  to R 6  are the same or different and are C 1-18  alkyl or C 1-18  oxaalkyl;   R F  is a fluorine atom, C 1-4  alkyl, C 1-4  oxaalkyl, or C 1-4  azaalkyl, wherein C 1-4  alkyl, C 1-14  oxaalkyl, C 1-4  azaalkyl are each perfluorinated,   with the proviso that if Z=O then R 7  is not NR 5 R 6 ,   and a salt soluble in said polar compound having an anion with a delocalized charge.   
   
   
       3 . The electrolytic composition according to  claim 2 , wherein the salt comprises at least one selected from the group consisting of I − , ClO 4   − , BF 4   − , AsF 6   − , SbF 6   − , PF 6   − , R F SO 3   − , XSO 2 NSO 2 X′ − , (XSO 2 )(X′SO 2 )(Y)C − , anionic derivative of 4,5-dicyano-1,2,3-triazole, 3,5-bis(R F )-1,2,4-triazole, tricyanomethane, pentacyanocyclopentadiene, pentakis(trifluoromethyl)cyclopentadiene, R F SO 2 NCN − , C(CN) 3   − , R F SO 2 C(CN) 2   − , and mixtures thereof, wherein
 X and X′ comprise at least one selected from the group consisting of R F , R F CH 2 O—, (R F ) 2 CHO—, or (R F CH 2 ) 2 N—, and R 8 , R 9 R 10 N—, with the proviso that at least one X or X′ is R F , R F CH 2 O—, (R F ) 2 CHO—, or (R F CH 2 ) 2 N—;   Y═R F , R F SO 2  or CN;   R F  is a fluorine atom, C 1-4  alkyl, C 1-4  oxaalkyl, or C 1-4  azaalkyl, wherein C 1-4  alkyl, C 1-4  oxaalkyl, C 1-4  azaalkyl are each perfluorinated and can be part of a macromolecular chain; and   R 8  to R 10  are the same or different, and are C 1-18  alkyl or C 1-18  oxaalkyl.   
   
   
       4 . The electrolytic composition according to  claim 3 , further comprising at least one cation selected from the group consisting of alkaline metal, alkaline earth metal, organic onium cation, ammonium, imidazolium, sulfonium, phosphonium, oxonium, and mixtures thereof. 
   
   
       5 . The electrolytic composition according to  claim 3 , further comprising at least one lithium cation. 
   
   
       6 . The electrolytic composition according to  claim 2 , further comprising a co-solvent. 
   
   
       7 . The electrolytic composition according to  claim 2 , further comprising at least one aprotic, polar co-solvent selected from the group consisting of dialkylethers of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol; carbonic acid ester; γ-butyrolactone; nitrile; tricyanohexane; dimethylformamide; N-methylpyrrolidinone; and mixtures thereof. 
   
   
       8 . The electrolytic composition according to  claim 2 , further comprising at least one polyethylene glycol co-solvent having a mass ranging from 400 to 2000 g/mol. 
   
   
       9 . The electrolytic composition according to  claim 2 , which comprises at least one polymer. 
   
   
       10 . The electrolytic composition according to  claim 2 , which comprises at least one polymer, wherein the polymer is a polyelectrolyte comprising a macromolecular chain and having a delocalized anionic charge. 
   
   
       11 . The electrolytic composition according to  claim 2 , which comprises at least one polymer, wherein the polymer is a homopolymer or copolymer comprising polymerized monomer units selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrine, epifluorohydrine, trifluoroepoxypropane, acrylonitrile, methylmethacrylate, vinylidene fluoride, N-vinylpyrrolidinone, hexafluoropropene, and mixtures thereof. 
   
   
       12 . The electrolytic composition according to  claim 2 , which comprises at least one polymer, wherein the composition is plasticized or in the form of a gel. 
   
   
       13 . An electrochemical generator, comprising at least one negative electrode, at least one positive electrode, and the electrolytic composition according to  claim 2 . 
   
   
       14 . The electrochemical generator according to  claim 13 , wherein the electrolytic composition comprises at least one co-solvent. 
   
   
       15 . The electrochemical generator according to  claim 13 , wherein the electrolytic composition comprises at least one polymer. 
   
   
       16 . The electrochemical generator according to  claim 13 , wherein the negative electrode comprises at least one selected from the group consisting of lithium metal, lithium alloy, carbon intercalation compound, oxide having a low potential of intercalation, double nitride of a transition metal and lithium, and mixtures thereof. 
   
   
       17 . The electrochemical generator according to  claim 16 , wherein the carbon intercalation compound is petroleum coke or graphite, and wherein the oxide having a low potential of intercalation is a titanium spinel. 
   
   
       18 . The electrochemical generator according to  claim 13 , wherein the positive electrode comprises at least one selected from the group consisting of vanadium oxide, mixed oxide of lithium and vanadium, oxide of cobalt and lithium, manganese spinel, double phosphate of the olivine or Nasicon structure, salt of rhodizonic acid, polydisulfide derived from the oxidation of 2,5-dimercapto-1,3,4-thiazole, 2,5-dimercapto-1,3,4-oxadiazole, 1,2-dimercaptocyclobutene-3,4-dione, and mixtures thereof. 
   
   
       19 . An supercapacitor-type energy storage system, comprising as an electrolyte the electrolytic composition according to  claim 13 , at least one polymer, and optionally a co-solvent. 
   
   
       20 . An electrochemical device, comprising as an electrolyte the electrolytic composition according to  claim 2 , and optionally a co-solvent, impregnated in one or more porous membranes.