Compositions – Electrolytes for electrical devices
Patent
1995-11-21
1999-06-29
Diamond, Alan
Compositions
Electrolytes for electrical devices
429306, 429307, 429304, 429310, 429321, 429199, 429188, 429189, 429324, 429339, 429340, 429341, 423383, 423386, 423365, 4234151, 423472, 423462, 4234991, 4234992, C08L 702
Patent
active
059164751
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an ionically conductive material, to its preparation and to its uses.
2. Description of the Background
Electrochemical systems for energy storage, for example batteries or supercapacities which operate with high elementary voltages, demand electrolytes which have an extensive range of stability. Such electrolytes are obtained by dissolving one or more solutes (1/mM').sup.+ X'.sup.- in a dipolar liquid solvent, a solvating polymer or their mixtures. M' is a cation of valency m, such as a proton, a cation derived from a metal (for example Li, Na, K, Mg, Ca, Cu, Zn or La) or an organic cation such as an ammonium ion, a guanidinium ion, a phosphonium ion or a sulphonium ion. Ionic compounds (1/mM').sup.+ X'.sup.- in which the anion X'.sup.- has a delocalized charge exhibit a high ionic conductivity. Among the X'.sup.- anions with a delocalized charge there may be mentioned I.sup.-, ClO.sub.4.sup.-, AsF.sub.6.sup.-, PF.sub.6.sup.-, R.sub.F SO.sub.3.sup.-, (R.sub.F SO.sub.2).sub.2 N.sup.-, R.sup.1 CO(CF.sub.3 SO.sub.2).sub.2 C.sup.- and R.sup.1 SO.sub.2 (CF.sub.3 SO.sub.2).sub.2 C.sup.-, R.sub.F denoting a perfluoroalkyl radical or a perfluoroaryl radical, R.sup.1 denoting a hydrogen atom, an alkyl radical, an oxaalkyl radical, an azaalkyl radical, an aryl radical, a perfluoroalkyl radical or a perfluoroaryl radical.
Although the abovementioned compounds may have high ionic conductivities, their use presents disadvantages. Iodide ions are easily oxidizable. Arsenic derivatives are toxic and perchlorates are explosive. Anions such as PF.sub.6.sup.-, capable of easily releasing a Lewis acid (PF.sub.6.sup.- .fwdarw.PF.sub.5) compromise the stability of the corresponding electrolytes via reactions causing the formation of electrophilic species of carbocation type.
Anions containing R.sub.F SO.sub.2 -- perfluorosulphonyl groups, in particular perfluorosulphonates R.sub.F SO.sub.3.sup.- and perfluorosulphonylimides (R.sub.F SO.sub.2).sub.2 N.sup.-, are stable and have low toxicity and the use of the corresponding ionic compounds has become generalized, especially for electrochemical generators including negative electrodes consisting of metallic lithium, a lithium alloy or a carbon-lithium intercalation compound. The preparation of these ionic compounds is, however, very costly, and the manufacture of compounds containing at least two perfluorosulphonyl groups very particularly so. Furthermore, these compounds have a high molecular mass and the mass fraction for a given molality in a solvent is large. F!.sup.- are known where (1/mM).sup.+ =H.sup.+, K.sup.+, Cs.sup.+, Chem. 4, 1446, (1965)!. In general, a salt constitutes an electrolyte which is proportionally better the lower the basicity of its anion. The which R.sub.F is a perfluoroalkyl group, because of the retrocession of the free pairs of the fluorine on the sulphur atom. Many publications report the fact that the substitution of a perfluoroalkyl group for a fluorine atom in an organic compound which is acidic in nature decreases the strength of the acid. (G. Paprott & K. Seppelt, J. Am. Chem. Soc., 106, 4060 (1984); E. D. Laganis, D. M. Lema, J. Am. Chem. Soc., 102, 6634 (1984); F. J. Bordwell, J. C. Branca et al., J. Org. Chem., 53, 780, (1988)).
Furthermore, it is known that the fluorine atom of an F--S bond is particularly labile and especially hydrolysable in the presence of water or of nucleophilic bases. Because of these disadvantages the use of the NSO.sub.2 R.sub.F !H such as H(CF.sub.3 SO.sub.2).sub.2 N or H(CF.sub.3 al., op. cit.; M. Razak et al., J. Appl. Electrochem., 136, 385 (1989)!.
It is also known that the compounds H(FSO.sub.2).sub.3 C are hydrolysed SO.sub.2).sub.3 C!.sup.- have been proposed as electrolyte solutes for electrochemical generators. However, just as in the case of the imides, the molecular mass and the costs of manufacture of the compounds their use of little interest.
JP-A-05 283 086 relates to a battery in which the electrolyte contains a c
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Armand Michel
Choquette Yves
Gauthier Michel
Michot Christophe
Sanchez Jean-Yves
Centre National de la Recherche Scientifique
Diamond Alan
Hydro-Quebec
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