MXPA01004122A - Monomers, ionomers and polymers for electrochemical uses - Google Patents

Abstract

Disclosed fluoro-olefins bearing an ionic functionality or a precursor thereto, a process for the production thereof, and polymers, especially ionomers, formed therefrom, and their application for electrochemical uses.

Description

MONOMERS, IONOMERS AND POLYMERS FOR ELECTROCHEMICAL USES DESCRIPTION OF THE INVENTION This invention is concerned with new fluoroolefins carrying an ionic functionality or a precursor thereof, a process for the production thereof and polymers, especially ionomers, formed from the same and their application in electrochemical cells in which are included batteries, fuel cells, electrolysis cells, ion exchange membranes, detectors, electrochemical capacitors and modified electrodes, more particularly in lithium batteries. The polymers of the invention are useful in the formation of films and coatings with high chemical resistance and good physical properties. The olefinic compositions of the invention are useful as monomer precursors to the polymers and ionomers of the invention, they are also useful in acid form, as superacid catalysts for reactions such as Friedel-Crafts alkylation.

BACKGROUND OF THE INVENTION He CF2 = CFCF2OCF2CF2S02F is described in Krespan, US Pat. No. 4,275,225. Also described are copolymers, in which terpolymers are included, with ethylenically unsaturated comonomers and the ionomers formed therefrom.

Ref: 127801 The preparation of CF2C1CFC1 (CF2CF2) 2I is described in U.S. Patent 5,350,821 issued Fearing et al. It has been known for a long time in the art how to form ionically conductive membranes and gels from organic polymers containing ionic pendant groups. Such polymers are known as ionomers. Particularly well-known ionomer membranes in commercially extensive use are Nafion® membranes available from E.l. du Pont de Nemours and Company. Nafion® is formed by the copolymerization of tetrafluoroethylene (TFE) with perfluoro (3,6-dioxa-4-methyl-7-octensulfonyl fluoride), as described in U.S. Patent 3,282,875. Also known are the copolymers of TFE with perfluoro (3-oxa-4-pentensulfonyl fluoride) as described in U.S. Patent 4,358,545. The copolymers thus formed are converted to the ionomeric form by hydrolysis, usually by exposure to an appropriate aqueous base, as described in U.S. Patent 3,282,275. Lithium, sodium and potassium are all well known in the art as suitable cations for the ionomers mentioned above. The formation of acid ionomers and copolymers by hydrolysis of the sulfonyl fluoride functionality in TFE copolymers and fluoroalkoxy sulfonyl fluoride is well known in the art. The technique teaches the exposure of the copolymer to strongly basic conditions. See, for example, U.S. Patent 4,940,525 issued to Ezzell et al, where NaOH is used. (aqueous) at 25% by weight for 16 hours at 80-90 ° C, US Patent No. 5,672,438 issued to Banerjee et al, where 25% by weight NaOH is used for 16 hours at 90 ° C or as an alternative , an aqueous solution of 6-20% alkali metal hydroxide and 5-40% polar organic liquid (for example, DMSO) for 5 minutes at 50-100 ° C; U.S. Patent 4,358,545 issued to Ezzell et al where 0.05 N NaOH is used for 30 minutes at 50 ° C; U.S. Patent 4,330,654 issued to Ezzell et al where 95% boiling ethanol is used for 30 minutes, followed by addition of an equal volume of 30% NaOH (aqueous) with continuous heating for 1 hour; European Patent EP 0345964 Al issued to Marshall et al, where 32% by weight NaOH (aqueous) and methanol are used for 16 hours at 72 ° C or alternatively, an aqueous solution of 11% by weight KOH and DMSO 30% by weight for 1 hour at 90 ° C and US Patent 5,595,676 issued to Barnes et al, where 20% by weight NaOH is used for 17 hours at 90 ° C.

Doyle et al (WO 98/20573) discloses a highly fluorinated lithium ion exchange polymer electrolytic membrane (FLIEPEM) exhibiting a conductivity of at least 0.1 mS / cm, which comprises a highly fluorinated lithium ion exchange polymer membrane (FLIEPM), the polymer has outstanding fluoroalkoxy lithium sulfonate groups and wherein the polymer is either completely or partially subjected to cation exchange and at least one aprotic solvent embedded in the membrane. Electrodes and lithium cells are also described. In the polymers mentioned above, the fluorine atoms provide more than one benefit. The fluorine groups on the carbons next to the sulfonyl group in the pendant side chain provide the electronegativity to render the cation sufficiently labile, to provide high ionic conductivity. The replacement of those fluorine atoms with hydrogen results in a considerable reduction in ionic mode and consequent loss of conductivity. The rest of the fluorine atoms, such as those in the polymer backbone, provide chemical and thermal stability to the polymer normally associated with the fluorinated polymers. This has proven to be of considerable value in such applications as the well-known "chlor-alkali" process. However, highly fluorinated polymers also have disadvantages where there is less need for high chemical and thermal stability. Fluorinated monomers are more expensive than their olefin counterparts, require higher processing temperatures and often require expensive corrosion resistant processing equipment. It is also difficult to form solutions and dispersions of fluoropolymers. Additionally, it is difficult to form strong adhesive bonds with fluoropolymers. In materials used in electrochemical cells, for example, it may be advantageous to have better processing capacity at some cost to the chemical and thermal stability. Thus, there is an incentive to develop ionomers with highly labile cations that have reduced fluoride content. Numerous publications describe polyethers with either nearby ionic species in the polymer or in combination with ionic salts. The conductivities are in the range of 10 ~ 5 S / cm and smaller. Le Nest et al, Polymer Communications 28, 303 (1987) describe a composition of polyether glycol oligomers linked by phosphorylated or thiophosphate moieties hydrolyzed to the related lithium ionomer. In combination with propylene carbonate, conductivity is carried out in the range of 1-10 x 10 ~ 4 S / cm. A review of the related art is found in Fauteux et al., Electrochimica Acta 40, 2185 (1995).

Benrabah et al., Electrochimica Acta, 40, 2259 (1995) describe polyethers crosslinked by lithium oxytetrasulfonates and derivatives. No aprotic solvent is incorporated. With the addition of lithium salts, a conductivity of < 10 ~ 4 S / cm. Armand et al., U.S. Patent 5,627,292 describe copolymers formed from vinyl fluoroethoxy sulfonyl fluorides or cyclic ethers having fluoroethoxy sulfonyl fluoride groups with polyethylene oxide, acrylonitrile, pyridine and other monomers. Lithium sulfonate ionomers are formed. No aprotic solvents are incorporated. The conductivity was < 10 ~ 4 S / cm. Narang et al., U.S. Patent 5,633,098 disclose polyacrylate copolymers having a fundamental functionalized polyolefin structure and pendant groups having tetrafluoroethoxy lithium sulfonate groups. The comonomers containing the sulfonate groups are present in molar proportions of 50-100%. Compositions comprising the polymer and a mixture of solvents consisting of propylene carbonate, ethylene carbonate and dimethoxy-triethylether are described. The ionic conductivity of those compositions was in the range of 10 ~ 4 - 10"3 S / cm In the present invention, both fully and partially fluoridated species are described.

BRIEF DESCRIPTION OF THE INVENTION This invention provides an olefinic composition represented by the formula: CF2 = CF (CF2CF2) nS02F 1 wherein n = 1 to 5. An ionizable olefinic composition represented by the formula is further provided: CF2 = CF (CF2CF2) nS03M where n = l to 5 and M is a univalent metal. A process for synthesizing 1 is further provided, the process comprising: reacting CF2C1CFC1 (CF2) nI, wherein n = 1-5 with Na2SO4 and NaHCO3 in a mixture of water and a polar aprotic solvent at a temperature in the range of room temperature at 110 ° C to form CF2C1CFC1 (CF2) nS02Na; reacting CF2C1CFC1 (CF2) nS02Na with Cl2 in water or a mixture of water and a polar aprotic solvent at a temperature in the range of 0-100 ° C to form CF2C1CFC1 (CF2) nS02Cl; reacting CF2C1CFC1 (CF2) nS02Cl with a univalent metal fluoride in an anhydrous polar aprotic solvent to form CF2C1CFC1 (CF2) nS02F; reacting CF2C1CFC1 (CF2) nS02F with Zn in an alcohol or a mixture of acetic acid and alcohol to form CF2 = CF (CF2) nS02F; and separate the product. Polymers are further provided in which ionomers are included, comprising 0.1 to 50 mol% of monomer units represented by the formula - CF -, - CF - I (CF2CF2) nS02 where n = 1 to 5, X is F u -OM where M is a univalent metal or hydrogen. There is further provided an ionomer comprising vinylidene fluoride monomer units and from 0.1 to 50 mol% of monomer units represented by the formula: -CF2-CF- (CF2) P-OCF2CF2SO3M wherein p is 1 to 10 and M is a univalent metal. The present invention further provides a process for forming a more suitable ionizable composition for use with base sensitive compositions such as those described herein. The process comprises contacting at a temperature in the range of 0-85 ° C a composition comprising the functional group - (CF2CF2) n-S02F wherein n is 1 to 5 with a solution of an alkali metal salt, the pH of the solution is not greater than 13, for a period of time sufficient to obtain the desired degree of conversion to the alkali metal sulfonate form of the polymer. The present invention further provides an ionically conductive composition comprising an ionomer of the invention and a liquid imbibed therein. The present invention further provides an ionically conductive composition comprising the ionizable olefinic composition of the invention and a liquid. The present invention further provides an electrode comprising at least one active electrode material and the ionomer of the invention. The present invention further provides an electrochemical cell comprising a positive electrode, a negative electrode, a separator disposed between the positive and negative electrodes and means for connecting the cell to an external load or source, wherein at least one of the group consisting of of the separator, the cathode and the anode comprises the ionomer of the invention.

DETAILED DESCRIPTION OF THE INVENTION This invention provides an olefinic composition represented by the formula: CF2 = CF (CF2CF2) nS02F wherein n is 1 to 5, preferably n is 1. The olefinic composition 1 is preferably used as a monomer in a free radical polymerization process. The process for synthesizing 1 comprises a first step of reacting CF2C1CFC1 (CF2CF2) nI with Na2S204 and NaHC03 in a mixture of water and a polar aprotic solvent at a temperature in the range of room temperature to 110 ° C to form CF2C1CFC1 (CF2CF2 ) nS02Na, n is 1 to 5, preferably n is 1. The polar aprotic solvent is preferably selected from the group consisting of acetonitrile, dimethylformamide (DMF), tetrahydrofuran (THF), dimethylsulfoxide (DMSO), dimethylacetamide (DMAC) ). Preferably, the temperature is in the range of room temperature to 50 ° C. Then the CF2C1CFC1 (CF2CF2) nS02Na thus produced is reacted with Cl2 in water or a mixture of water and a polar aprotic solvent at a temperature in the range of 0-200 ° C, preferably 5-100 ° C, more preferably 25-100 ° C to form CF2C1CFC1 (CF2CF2) nS02Cl. The aprotic polar solvent is preferably selected from the group mentioned hereinabove. Then CF2C1CFC1 (CF2CF2) nS02Cl is reacted with a univalent metal fluoride in an anhydrous polar aprotic solvent at a temperature of 0-100 ° C, preferably 20-50 ° C to form CF2C1CFC1 (CF2CF2) nS02F. Preferably, the univalent metal is an alkali metal, more preferably potassium. Preferably, the polar aprotic solvent is selected from the group mentioned above herein. The CF2C1CFC1 (CF2CF2) nS02F is reacted with Zn in alcohol or a mixture of acetic acid and alcohol at a temperature in the range of 30-150 ° C, preferably 50 ° C to 100 ° C to form CF2 = CF (CF2CF2 ) nS02F. The alcohol is preferably ethanol or isopropanol. More preferably, the solvent is a mixture of acetic acid and isopropanol. The final sulfonyl fluoride product can be separated by any convenient method known in the art, such as by distillation or recrystallization. The olefinic composition 1 can be copolymerized according to means known in the art to polymers having 0.1 to 50 mol% of monomer units represented by the formula: ~ CF, -CF- I • (CF2CF2) RS02F where n = 1 5. The polymer 2 is preferably used as a thermoplastic precursor to an ionomer, but can also be used as a coating or film-forming resin. Krespan, US Pat. No. 4,275,225 teaches the formation of polymers and copolymers from a monomer represented by the formula: CF2 = CF (CF2CF2) n-0CF2CF2S02F the teachings include ethylenically unsaturated comonomers, TFE is preferred. The teachings of Krespan can be extended to the copolymerization of the olefinic composition 1 of the present invention to form the polymer of the present invention. Suitable monomers for use in forming the copolymers of the invention include any ethylenically unsaturated compound that is copolymerizable by a free radical polymerization process. Preferred monomers include ethylene, propylene, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), trifluoroethylene, vinylidene fluoride (VF2) and vinyl fluoride. More preferred are ethylene and VF2. Mixtures of monomers are also suitable for the formation of terpolymers of the invention. Preferred mixtures of monomers include VF2 and HFP, VF2 and CTFE, TFE and ethylene, VF2 and TFE and VF2 and trifluoroethylene. The most preferred mixtures are VF2 / HFP, TFE / E, CTFE / E.

The exact degree of incorporation of comonomers in the polymer will be dependent on the relative reactivities of the respective monomers under the reaction conditions. The polymers of the invention are mainly random copolymers having 0.1 to about 50 mol%, preferably 1 to 20 mol%, more preferably 3-12 mol% of the sulfonyl-containing monomer unit incorporated therein. Polymers that contain some degree of block copolymer character are encompassed by the present invention but are less preferred. It is desirable for the purposes of the present invention, ie the formation of useful components in lithium batteries, to incorporate about 3-12 mol% of the ionizable monomer units or their precursors into the polymer. When TFE is used as the comonomer with the monomer of the invention 1, the degree of incorporation of 1 tends to be less than about 3 mol%. One means to improve the degree of incorporation is to employ VF2 or a comonomer instead of TFE. This results in the rapid incorporation of about 3-12% in mol of 1. Copolymers of 1 with VF2 tend to exhibit excessive crystallinity, particularly at the lower concentration end of 1. The high crystallinity is undesirable because it affects negatively conductivity and hardness. Thus, the incorporation of a thermonomer that alters the crystallinity, such as HFP is desirable. Alternatively, a similar balance between incorporation and crystallinity can be obtained by producing a terpolymer of 1 with ethylene and TFE. The polymerization can be carried out by block polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Bis (perfluoropropionyl) peroxide and bis (4-t-butylcyclohexylperoxy) bicarbonate are free radical initiators suitable for suspension polymerization or solution polymerizations. In aqueous polymerization, inorganic peroxides such as ammonium or potassium persulfate have been found suitable. In aqueous polymerization it is preferred to employ surfactants such as perfluorocarboxylic salts, C7F? 5C02NH4 is more preferred. Other initiators such as are known in the art are also suitable for use. The copolymers of the present invention having monomer units represented by formula 2 can be mostly hydrolyzed to form the ionomers of the present invention by methods known in the art. However, in the preferred embodiments wherein VF2 is present in amounts of 10 mol% or greater, the methods taught in the art can not be put into operation.

In one embodiment, the ionomers of the present invention comprise 0.1 to 50 mol% of monomer units represented by the formula: -CF2-CF- (CF2CF2) "S03X wherein n = 1 to 5 and X is hydrogen or a univalent metal. Preferably n = 1 and X is Li. Preferred ionomers of the invention comprise monomer units of VF2 and 0.1 to 50 mol% of monomer units represented by the formula: -CF2-CF-Rf-S03M wherein Rf is represented by the formula: - (CF2) p- (OCF2CF2) m- where p is 1 to 10 and m = 0 or 1, with the proviso that when m = 0, p is an even number. Preferably p is 1 and m = 1. M is a univalent metal or hydrogen, preferably M is an alkali metal; more preferably M is Li. When m = 1, monomer 3 is synthesized according to the teachings of Krespan op. cit. Methods taught in the art to hydrolyze sulfonyl fluoride to a sulfonate salt involve the use of strong bases at temperatures well above room temperature. Such methods are highly effective when applied to polymers having fundamental chemically inert structures. However, the methods of the art applied to less stable species result in extensive degradation. It is known in the art that VF2 homopolymers and copolymers are subject to attack by strong bases such as the alkali metal hydroxides taught in the hydrolysis processes of the art, see W.W. Schmiegel in Die Angewandte Ma romole ulare Chemie, 76/77 pp 39ff, 1979. The base attack sensitivity of the VF2 copolymer formed in the practice of the present invention has impeded the development of a single ionic conductive ionomer based on VF2. There is simply no means taught in the art to make the ionomer. The present invention further provides a process for forming a more suitable ionizable composition for use with base sensitive compositions such as those described herein. The process comprises contacting at a temperature in the range of 0-85 ° C a composition comprising the functional group - (CF2CF2) n-S02F where n = 1 to 5 with a solution of an alkali metal salt or hydroxide , the pH of the solution is not greater than 13, for a period of time sufficient to obtain the desired degree of conversion to the alkali metal sulfonate form of the polymer.

The base unstable species suitable for use in the hydrolysis process of the invention include species comprising - (CF2CF2) n-S02F where n = 1 to 5 and unsaturated carbon-carbon bonds such as 1 or 3 and fluoride-containing copolymers of sulfonyl comprising vinylidene fluoride, in which copolymers or terpolymers of 1 or 3 are included with vinylidene fluoride. It is a surprising result of the hydrolysis process of the invention that there are conditions wherein the desired hydrolysis can be carried out in the absence of the undesirable side reactions characteristic of the hardest conditions employed in the art. It will be understood by one skilled in the art that there are different degrees of instability to the base in the preferred base-sensitive species for the practice of the hydrolysis process of the invention. For example, a vinyl ether copolymer with vinylidene fluoride is more susceptible to base attack than a vinylidene fluoride copolymer not containing vinyl ether. The skilled artisan will appreciate that the hydrolysis can not proceed unless there is contact between the hydrolyzing solution and the hydrolyzable species. Such contact can be obtained in solution in a common solvent, by finely subdividing a solid, such as a polymeric, hydrolysable species or by causing a hydrolysable polymer to expand or swell when using solvent for the hydrolyzing solution which are also soluble in the polymer . In general, more moderate hydrolysis conditions consisting of the timely conversion of the sulfonyl fluoride to the desired ionic form are preferred. The degree of conversion can be conveniently verified by the disappearance of the characteristic infrared absorption band for the sulfonyl fluoride group at about 1470 cm-1. Alternatively, 19 F NMR spectroscopy can be used as described in the examples. A preferred hydrolysis process of the invention comprises contacting the monomer or polymer containing sulfonyl fluoride with a mixture of alkali metal carbonate and methanol at a temperature in the range of room temperature to 65 ° C for a duration of time sufficient to convert the desired percentage of sulfonyl fluorides to the related metal sulfonate. The alkali metal carbonate is selected to provide the desired cation for the proposed application. Suitable alkali metal carbonates include Li 2 CO 3, Na 2 CO 3 and K 2 CO 3, Li 2 CO 3 is more preferred. Other cationic forms of the ion exchange membrane can be obtained using ion exchange methods commonly known in the art (see for example Ion Exchange by F. Helfferich, McGraw Hill, New York, 1962). For example, the protonic form of the membrane is preferably obtained by immersing the alkali metal ionomer in an aqueous acid. The silver and copper sulfonate ionomers can be made by ion exchange with the alkali metal sulfonate form of the polymer. For example, repeated treatment of the lithium sulfonate ionomer with an aqueous solution of a silver salt, such as silver fluoride or silver perchlorate, would produce at least one silver sulfonate ionomer partially ion-exchanged. Similarly, the cuprous sulfonate ionomer can be produced by the repeated treatment of the alkali metal sulfonate ionomer with an aqueous acid solution of a copper salt such as cuprous chloride. In many applications, the ionomer is preferably formed in a film or sheet. Films of the ionomers can be formed according to processes known in the art. In one embodiment, the polymer containing thermoplastic sulfonyl fluoride is molten in the molten state by extrusion on a cooled surface such as a rotating drum or roller, where it is subjected to hydrolysis according to the process described hereinabove.

In a second embodiment, the sulfonyl fluoride-containing polymer is dissolved in a solvent, the solution is poured onto a smooth surface such as a glass plate using a mixing blade or other device known in the art to assist in depositing the film on a substrate and the resulting film is subjected to hydrolysis. In a third embodiment, the resin of the copolymer containing sulfonyl fluoride is subjected to hydrolysis by dissolution or suspension in a hydrolyzing medium, followed by optional addition of cosolvent and filtration or centrifugation of the resulting mixture and finally solvent discharging from the solution of ionomer on a substrate using a mixing blade or spatula or other device known in the art to help deposit films onto a substrate. The sulfonyl fluoride-containing copolymer may exhibit a tendency to dissolve during hydrolysis when the concentration of the sulfonyl fluoride portion is greater than about 5 mol%. Thus, for the purpose of obtaining better control over the film-forming process, it is preferable to suspend the precursor polymer containing non-ionic sulfonyl fluoride in a solvent or combination of solvents such as methanol, dimethyl carbonate or mixtures thereof. which also contain the hydrolyzing agent, preferably Li2C03, thereby hydrolyzing the polymer in solution. Then the polymer thus hydrolyzed is molded as a solution film. The ionomer of the present invention thus formed, exhibits a low level of ionic conductivity in the dry state, at room temperature, usually around 10 ~ 6 S / cm. It can be combined with a liquid to obtain higher levels of ionic conductivity. Depending on the requirements of the application, the ionomer will be in acid form or the metal salt form, the particular metal is determined by the application as well. The liquid used with it will also be determined by the application. In general terms, it has been found in the practice of the invention, that the conductivity of the ionomer containing the liquid increases with the absorption in increased% by weight, increasing the dielectric constant and increasing the Lewis basicity of the liquid, while it has been observed that the conductivity decreases with the increased viscosity and the increased molecular size of the liquid used. Of course, other considerations also come into play. For example, the excessive solubility of the ionomer in the liquid may be undesirable or the liquid may be electrochemically unstable in the proposed use.

In a preferred embodiment of the present invention, the lithium ionomer is combined with an aprotic solvent to form a conductive composition suitable for use in lithium batteries. Preferred aprotic solvents include dimethyl sulfoxide, ethylene carbonate, propylene carbonate, dimethoxyethane, gamma-butyrolactone, mixtures thereof and mixtures thereof with dimethyl carbonate. More preferred is a mixture of ethylene carbonate and dimethyl carbonate. A particularly preferred embodiment comprises the lithium ionomer comprising VF2 monomer units combined with aprotic solvents, preferably organic carbonates. It is in lithium batteries that the particularly useful attributes of the ionomer of the invention are particularly remarkable. The high solvent absorption characteristic of the VF2 polymers results in a desirably high ionic conductivity in the swollen or solvent dilated membrane. In addition, the VF2 imparts highly desirable electrochemical stability in the lithium battery environment. It has been found in the practice of the invention that an ionomer of the invention containing at least 50% of VF2, more preferably at least 80% of VF2 can become excessively plasticized by the solvents embedded therein, with the concomitant loss of the physical integrity of the membrane. In some applications it may be desirable to improve the properties of the solvent-expanded membrane. Means available to improve the chemical properties include: (1) incorporation into the polymer by means known in the art and following the synthetic route described hereinafter, of a third nonionic monomer that is less sensitive to the solvent; (2) formation by known means of a polymeric combination with a nonionic polymer that is less sensitive to the solvent; (3) combination by known means of the ionomer of the invention with an inert filler; (4) combination of different compositions of the ionic copolymers and (5) crosslinking. Suitable third monomers include tetrafluoroethylene, chlorotrifluoroethylene, ethylene, hexa-fluoropropylene, trifluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride, perfluoroalkylvinyl ethers of the formula: CF2 = CF0Rf where Rf = CF3, C2F5 or C3F6. Preferred thermonomers include tetrafluoroethylene, hexafluoropropylene, ethylene and the perfluoroalkylvinyl ethers. The thermonomers are preferably present in the polymer in a concentration of up to 30 mol%. Suitable polymers for combination with the preferred ionomers of the invention include poly (tetrafluoroethylene) and copolymers thereof with hexafluoropropylene or perfluoroalkyl vinyl ethers, polyvinylidene fluoride homopolymer and a copolymer thereof with hexafluoropropylene, polymethyl methacrylate, polyethylene oxide and poly (vinyl chloride). vinyl). A preferred composition comprises 25 to 50% by weight of PVF2 homopolymer combined with the preferred ionomer of the present invention. These materials are easily combined together by common means in the art, such as dissolution and mixing in a common solvent such as acetone and then molding a membrane. Suitable inert fillers include Si02, A1203, Ti02 or CaF2. Particles of small and high surface area less than 1.0 micron in diameter are desirable, as are available for the preferred grade of Si02 under the trade name silica Cab-o-Sil® TS-530. Loads of up to 50% by weight filler are preferred. The relatively high solubility of the preferred ionomers of the present invention and their sulfonyl fluoride precursors provide a benefit of processing ease during the manufacture of the components of a battery, but can be problematic during the final assembly of the desired battery product. In a preferred embodiment of the battery of the present invention, a battery is formed from one or more electrochemical cells formed by laminating together in film form the anode, cathode and spacer compositions of the present invention, all of which have After being thoroughly dried before the addition of a liquid selected from the group of organic carbonates and mixtures thereof, a mixture of ethylene carbonate and dimethyl carbonate is more preferred. The organic carbonates will not only dilate the ionomeric polymer, but may also dissolve the polymer depending on the composition thereof, the primary determining factor is the degree of crystallinity, which in turn is related to the concentration of the ionic monomer in the polymer. The challenge is to dilate the ionomer with solvent while minimizing polymer dissolution. One way to obtain the necessary balance is to use the methods described hereinabove to improve the physical integrity of the ionomer containing the solvent. Another method comprises dissolving the ionomer in preferred organic carbonate solvents, followed by introducing the resulting solution into the pores of an inert porous polymeric support such as porous polypropylene Celgard®, available from Hoechst-Celanese or Gore-Tex microporous PTFE, available of WL Gore Associates, Newark, DE.

The preferred electrode of the invention comprises a mixture of one or more active particulate electrode materials, the ionomer of the invention, at least one electron-conducting additive and at least one organic carbonate. Examples of useful anode active materials include, but are not limited to carbon (graphite, coke, mesocarbons, polyacenes and the like) and carbon intercalated with lithium, lithium metal nitrides such as Li2.6C? N.4N, oxides tin, lithium metal and lithium alloys, such as lithium alloys with aluminum, tin, magnesium, mercury, manganese, iron and zinc. Lithium intercalation anodes that use carbon are preferred. Useful cathode active materials include, but are not limited to, transition metal oxides and sulfides, lithium transition metal oxides and sulfides, and sulfoxides and organosulfur compounds. Examples of such are cobalt oxides, manganese oxides, molybdenum oxides, vanadium oxides, titanium sulfides, molybdenum and niobium, lithiated oxides such as spinel of lithium manganese oxides Li? + XMn2_x04, oxides of manganese spinel lithium doped with chromium LixCryMn204, LiCo02, LiNi02, LiNixC ?? - x02 where x is 0 < x < 1, with a preferred range of 0.5 < x < 0.95, LIC0VO4 and mixtures thereof. LiNixC ?? - x02 is preferred. A highly preferred electron-withdrawing helper is carbon black, preferably carbon black super P, available from MMM, S.A. Coal, Brussels, Belgium, in the concentration range of 1-10%. Preferably, the volume fraction of the lithium ionomer in the finished electrode is between 4 and 40%. The electrode of the invention can be conveniently made by dissolving all the polymeric components in a common solvent and mixing together with the carbon black particles and active electrode particles. For cathodes, the preferred electrode active material is LiNixC _ x02 where 0 <1. x < 1, wherein for the anodes the preferred electrode active material consists of graphitized mesocarbon microbeads. For example, a preferred lithium battery electrode of the invention can be manufactured by dissolving the ionomer of the invention in a mixture of acetone and dimethylformamide, followed by addition of particles of the electrode and carbon black active material, followed by deposition of a film on a substrate and dried. The resulting preferred electrode will comprise active electrode material, conductive carbon black and the ionomer of the invention, wherein, preferably, the weight ratio of the ionomer to the active electrode material is between 0.05 and 0.8 and the weight ratio of the Carbon black to the electrode active material is between 0.01 and 0.2. More preferably, the weight ratio of the ionomer to the active electrode material is between 0.1 and 0.25 and the weight ratio of carbon black to the active electrode material is between 0.02 and 0.1. Then this electrode can be molded of solution onto a suitable support such as a glass plate or current collector metal sheet and formed into a film using techniques well known in the art. The electrode film thus produced can then be incorporated into a multilayer electrochemical cell structure by lamination, as described hereinafter. It may be desirable to incorporate additional polymers or solvents into the electrode composition of the invention for purposes such as improving the agglutination of the components thereof or providing improved structural integrity of an article made therefrom. A particularly preferred additional material is polyvinylidene fluoride homopolymer, which can be incorporated simply by dissolving the polymer in the same solution from which the electrode is formed, as described hereinabove. In an alternative process, the dispersion of the optional electrode and optional carbon black material and other adjuvants can first be molded onto a surface followed by addition of the ionomer of the invention in organic carbonate solution.

The invention is further described in the following specific embodiments.

EXAMPLES EXAMPLE 1 To a stirred solution at room temperature of 157 grams of Na2S204, 75.6 grams of NaHCO3 in 400 ml of acetonitrile and 400 ml of water is added dropwise 227.6 g of CF2C1CFC1CF2CF2I, which was synthesized according to the teachings of Feiring et al. to, U.S. Patent 5,350,821. After the addition was complete, the resulting mixture was stirred overnight. The solids were separated by filtration and washed with ethyl acetate. The filtrate was extracted with ethyl acetate three times. The combined organic layers were washed with aqueous NaCl solution and evaporated to give 200 grams of the crude salt, which was dissolved in 700 ml of water and treated with chlorine at 5 ° C for two hours. The light yellow organic layer was separated and washed with aqueous NaCl solution and dried over MgSO4. After separation of MgSO4, the organic layer was distilled to give the product of CF2C1CFC1CF2CF2S02 146.3 grams. A mixture of 135 grams of the CF2C1CFC1CF2CF2S02C1 thus produced and 40 grams of KF in 200 ml of acetonitrile was stirred at room temperature for 24 hours and at 50 ° C for 6 hours. The mixture was poured into water and the lower layer was separated and washed with water and aqueous NaCl solution to give 117.5 g of product CF2C1CFC1CF2CF2S02F 99.5% pure. To a stirred suspension of 30 grams of Zn and 35 ml of isopropyl alcohol and 45 ml of acetic acid are added slowly 77 grams of CF2C1CFC1CF2CF2S02F thus produced at 90 ° C. After the addition was complete, the reaction mixture was stirred for 8 hours. The volatiles were distilled and the distillate was poured into water. The lower layer was separated, washed with NaHC03 solution and water and distilled to give 27.3 grams of CF2 = CFCF2CF2S02F, boiling point 72 ° C. NMR 19F: +45.1 (s, 1F), -85.0 (dd, J = 45.2hz, J = 37.7Hz, 1F), -102.7 (dd, J = 45.2Hz, J = 124.3Hz, 1F), -110.4 ( d, J = 3.8Hz, 2F), -116.0 (m, 2F), -190.0 (ddt, J = 124.3Hz, J = 22.6Hz, J = 3.8Hz, 1F).

EXAMPLE 2 Following the teachings of U.S. Patent 4,275,225 issued to Krespan, to a stirred suspension of 37.7 g of KF and 500 ml of TG are rapidly added 108 g of FC0CF2S02F at 0 ° C and the resulting mixture was stirred at 0 ° C during 20 minutes. 150 g of CF2 = CFCF20S02F are slowly added to the solution via an addition funnel at a temperature of -5 to 0 ° C for 1.5 hours. After the addition was complete, the mixture was stirred at -5 ° C for 1 hour and then warmed to room temperature for 2 hours. The volatiles were transferred to a trap at -78 ° C under vacuum. CF2 = CFCF20CF2CF2S02F 97% pure 188.5 g is obtained. NMR 19F: +45.1 (pent, J = 6.0Hz, 1F), -71.5 (m, 2F), -82.6 (, 2F), -89.9 (ddt, J = 54.3Hz, J = 39, J = 7.4Hz, 1F), -103.7 (ddt, J = 117.9Hz, J = 117.9Hz, J = 54.3Hz, J = 25.3Hz, 1F), -112.5 (t, J = 2.6Hz, 2F), -190.7 (ddt, J) = 117.Hz, J = 39.0Hz, J = 14Hz, 1F). A 240 ml shaker tube was charged with 100 ml of 1,1-trichloro-trifluoroethane (F113), 12 g of CF2 = CFCF20CF2CF2S02F thus produced and 0.34 g of bis (4-t-butylcyclohexylperoxy) Perkadox ™ dicarbonate obtained of Pennwalt Chemical Corp. now extinct. The reaction vessel was cooled in dry ice and degassed and replaced with nitrogen gas repeatedly. 36 g of vinylidene fluoride was added to the vessel and the tube was heated at 50 ° C for 10 hours and 80 ° C for 2 hours. After completion of the polymerization, the unreacted VF2 was removed and the white solid was dissolved in 500 ml of acetone. The acetone solution was slowly poured into MeOH. The solid was filtered and washed with MeoH and dried in a partial vacuum oven at 80 ° C to give 38.2 g of polymer. IR (KBr): 1463 c "1 (S02F) NMR 19F indicated approximately 5 mol% CF2 = CFCF2OCF2CF2S03F Elemental analysis indicated 3.3 mol% CF2 = CFCF2OCF2CF2S02F based on C 34.7% and H 2.70%, PM = 4.1xl0"4 and NM = 8.6xl03 The DSC showed that the polymer had a Tm of 146 ° C. The decomposition temperature was 400 ° C by TGA in N2 A suspension solution of 3.0 g of copolymer Thus, 1.0 g of LiC03 in 15 ml of water and 15 ml of MeOH was stirred for 2 days and then diluted with 100 ml of water.The solid was filtered and washed with water and dried in an oven at 80 ° C to give 2.67 g of white polymer that was soluble in DMAc 19 F NMR did not indicate sulfonyl fluoride The polymer could be pressed into a thin film The TGA indicated that the decomposition temperature was 250 ° C and the DSC showed a Tm at 140 ° C.

EXAMPLE 3 A 240 ml shaker tube was charged with 100 ml of 1,2-trichlorotrifluoroethane (F113), 12 g of CF2 = CFCF2OCF2CF2S02F made in example 2 and 0.24 g of bis (4-t-butylcyclohexylperoxy) dicarboxylate Perkadox ™ The reaction vessel was cooled in dry ice and degassed and replaced with nitrogen gas repeatedly. 18 g of vinylidene fluoride was added to the vessel and the tube was heated at 50 ° C for 10 hours and 80 ° C for 2 hours. After completion of the polymerization, the unreacted VF2 was removed and the white solid was dissolved in 400 ml of acetone. The acetone solution was slowly poured into a 1: 1 MeOH and water solution. The solid was filtered and washed with MeOH and dried in a partial vacuum oven at 80 ° C to give 16.2 g of polymer. IR (KBr): 1460 cm-1 (S02F). The elemental analysis indicated 7.3% in mol of CF2 = CFCF2OCF2CF2S02F based on C, 32.1% and H 2.14% and 19F NMR (CD3COCD3) indicated 8.4% in mol of CF2 = CFCF2OCF2CF2S02F: +45.7 (s, S02F), -76.5 (d, J = 147Hz), -78.1 (d, J = 147Hz), -81.6 (s), -91 (m), -111.6 (s), -110 to -117 (m), -183.6), PM = 8.8xl04 and NM = 2.7xl04. The DSC demonstrated that the polymer had a TM of 123 ° C. The decomposition temperature was 400 ° C by TGA in N2. A mixture of 2.8 g of the polymer thus prepared, 10 ml of saturated LiOH in 50 ml of water and 50 ml of MeOH was stirred at room temperature for 2 days. After being diluted with 200 ml of water, the mixture was filtered and washed with water 5 times and dried at 70 ° C in a partial vacuum oven to give ionic polymer 2.7 g. 19 F NMR indicated the complete conversion of the sulfonyl fluoride group to the lithium salt of sulfonic acid.

EXAMPLE 4 A 240 ml shaker tube was charged with 100 ml of 1,2-trichlorotrifluoroethane (F113), 12 g of the CF2 = CFCF2OCF2CF2S02F of Example 2 and 0.34 grams of Perkadox ™. The reaction vessel was cooled in. Dry ice and degassed and replaced with nitrogen repeatedly. 36 g of vinylidene fluoride and 7 g of HFP were added to the vessel and then the tube was heated at 50 ° C for 10 hours and 80 ° C for 2 hours. After completion of the polymerization, the unreacted VF2 and HFP were removed and the white solid was dissolved in 400 ml of acetone. The acetone solution was slowly poured into 800 ml of stirred MeOH. The solid was filtered and washed with MeOH and dried in a partial vacuum oven at 80 ° C to give 35.5 g of the polymer. IR (KBr) 1460 (S02F). The elemental analysis indicated 2.6% in mol of CF2 = CFCF2OCF2CF2S02F and 8% in mol of HFP based on C, 33.30% and H, 2.30%. The CPG showed PM = 1.3xl05 and NM = 4.9xl04. The DSC showed that the polymer had a broad Tm, 140 ° C. The decomposition temperature was 400 ° C by TGA in N2. A suspension of 10.6 g of polymer thus produced, 2.3 g of Li2C03 in 70 ml of MeOH and 2 ml of H20 was stirred at room temperature for 5 hours and at 50 ° C for 24 hours. After being diluted with water, the suspension was filtered, the solid was washed with water for 10 times and dried in a partial vacuum oven at 80 ° C for two days. 8.12 g of a bleached white polymer are obtained. The NMR of 19 F in acetone does not indicate any group of S02F.

EXAMPLE 5 A 240 ml shaker tube was charged with 100 ml of 1,2-trichlorotrifluoroethane (F113) 6 g of CF2 = CFCF20CF2CF2S02F of example 2 and 0.34 g of Perkadox ™. The reaction vessel was cooled in dry ice and degassed and replaced with nitrogen gas repeatedly. 20 g of TFE and 8 g of ethylene were added to the reaction vessel and then the tube was heated at 50 ° C for 10 hours. After completion of the polymerization, the unreacted monomers were removed and the white solid was washed with MeOH and acetone and dried in a partial vacuum oven at 80 ° C to give 23.5 g of the polymer. IR (KBr) 1454 and 1472 cm "1 (S02F) The DSC showed that the polymer had a broad Tm of 223 ° C and an acute Tm of 243 ° C. The decomposition temperature was 400 ° C by TGA in N2. A melt-pressed film of the polymer thus prepared was immersed in a saturated solution of LiOH of water and MeOH 1: 1 at room temperature for 7 days.After being washed with water, the film was immersed in water and MeOH 1: 1. at room temperature for 1 day, then washed with MeOH and dried in a partial vacuum oven at 80 ° C for 2 days.

EXAMPLE 6 A 240 ml shaker tube was charged with 100 ml of 1,1,2-trichlorotrifluoroethane (F113), 6 g of CF2 = CF2CF2S02F of example 1 and 0.17 g of Perkadox ™. The reaction vessel was cooled in dry ice and degassed and replaced with nitrogen gas repeatedly. 12 g of vinylidene fluoride is added to the container and then the tube was heated at 50 ° C for 12 hours. After completion of the polymerization, the unreacted VF2 was removed and the white solid was dissolved in acetone. The acetone solution was poured slowly into stirred MeOH. The solid was filtered and washed with MeOH and dried in a partial vacuum oven at 80 ° C to give 10.0 g of the polymer. IR (KBr) 1460 (S02F).

EXAMPLE 7 A 240 ml shaker tube was charged with 100 ml of 1,2-trichlorotrifluoroethane (F113), 5 g of CF2 = CFCF2CF2S02F from Example 1 and 0.17 g Perkadox 'TM The reaction vessel was cooled in dry ice and degassed and replaced with nitrogen gas repeatedly. 18 g of vinylidene fluoride and 3.5 g of HFP were added to the vessel and then the tube was heated at 50 ° C for 10 hours and 80 ° C for 2 hours. After completion of the polymerization, the unreacted VF2 and HFP were removed and the white solid was dissolved in acetone. The acetone solution was poured slowly into stirred MeOH. The solid was filtered and washed with MeOH and dried in a partial vacuum oven at 80 ° C to give 18.4 g of the polymer. IR (KBr): 1460 (S02F) cm_1. MW = 1.0 x 105 and NM = 3.6 x 104. The polymer had a broad Tm peak at 135 ° C. The decomposition temperature was 400 ° C in nitrogen by TGA in N2.

EXAMPLE 8 A suspension of 5.8 g of the polymer made in Example 7, 25 ml of saturated LiOH and 30 ml of MeOH were stirred at room temperature for 36 hours. After being diluted with 200 ml of water, the suspension was filtered, the solid was washed with water and MeOH and dried in an oven at 70 ° C to give 5.4 g of bleached white polymer. 19 F NMR indicated complete conversion of the sulfonyl fluoride group to the lithium salt of sulfonic acid.

EXAMPLES 9-11 In Examples 9-11, conductive compositions comprising hydrolyzed polymeric films and organic carbonates are exemplified. The ionic conductivity was determined using the so-called four-point sample technique described in an article entitled "Proton Conductivity of Nafion® 117 As Measured by a Four-Electrode AC Impedance Method" by Y. Soné et al., J. Electrochem. Soc., 143, 1254 (1996). The method as described is applied to aqueous electrolytic membranes. The method was modified for purposes of obtaining the measurements depicted herein for non-aqueous solvents by placing the described apparatus in a sealed glovebox purged with anhydrous nitrogen in order to minimize any exposure to water. The method was also modified by substituting parallel linear samples that run the full width of the test sample for the point samples used in the published method. The hydrolyzed polymer was formed into films by pressing in a laboratory hydraulic press at 210 ° C and 21.1 kg / cm2 (3000 pounds per square inch) of pressure. A 1.0 cm x 1.5 cm film was dried and positioned in the conductivity cell. The impedance of the cell was determined in the range of 10 Hz to 100,000 Hz and the value with the phase angle 0 in the higher frequency range (usually 500-5000 Hz) was attributed to the resistance of the global sample in ohms . Then the approximate resistance value was converted to conductivity, in S / cm, using the cell constant and the swollen film thickness of liquid.

EXAMPLE 9 A sample of approximately 2.5 cm x 2.5 cm (2"x 2") of the film of the hydrolyzed polymer of Example 2 was dried in a recirculating nitrogen oven (Electric Hotpack Company, Inc., Model 633, Philadelphia, PA) at 100 ° C for 24 hours. The dried membrane was transferred to a sealed container while it is still warm and transported to a glove box that has a positive pressure of dry nitrogen applied to it, where the membrane was removed from the sealed container and allowed to reach room temperature. The membrane was cut into several sections of 1.0 cm by 1.5 cm in size. Then a cooled 1.0 cm by 1.5 cm membrane sample was rinsed in an excess of a 1: 1 by volume mixture of ethylene carbonate (EC, Selectipur, EM industries, Inc., Hawthorne NY) and dimethyl carbonate (DMC, Selectipur, EM Industries) in a sealed glass jar for two hours at room temperature. The membrane was removed from the solvent bath, dried with a paper towel to remove excess solvent and tested using the four-point sample test described above. The conductivity was 5.91 x 10"4 S / cm.

EXAMPLE 10 An additional 1.0 cm by 1.5 cm cooled membrane sample from Example 9 was rinsed in an excess of propylene carbonate (PC, Selectipur, EM Industries) in a sealed glass jar for 2 hours at room temperature. The membrane was removed from the solvent bath, dried with a paper towel to remove the excess solvent and tested using the four-point sample test described above. The conductivity was 1.62xl0 ~ 4 S / cm.

EXAMPLE 11 A 1 liter autoclave was charged with 300 ml of 1,1-trichlorotrifluoroethane (F113), 14 g of CF2 = CFCF2OCF2CF2s02F of example 2 and 0.30 g of Perkadox ™. The reaction vessel was cooled in dry ice and degassed and replaced with nitrogen gas repeatedly. 14 g of TFE and 20 g of ethylene are added to the vessel and then the tube was slowly heated to 50 ° C and maintained at 50 ° C for 10 hours. After completion of the polymerization, the unreacted monomers were removed and a white suspension was obtained. After removal of the solvent, the white solid was washed with MeOH and dried in a partial vacuum oven at 75 ° C to give 24.8 g of the polymer. IR (KBr) 1454 and 1472 cm "1 (S02F) The DSC showed that the polymer had a broad Tm at 175 ° C. The decomposition temperature was 380 ° C by TGA in nitrogen in N2 A suspension of 3.8 g of the polymer thus produced and 2.5 g of LiOH in 10 ml of MeOH, 10 ml of water and 80 ml of DMSO was stirred at 80 ° C. for 5 hours.The reaction mixture was slowly poured into 500 ml of stirred MeOH and water. : 1 and filtered to give a solid, which was washed with MeOH several times and dried in an oven at 70 ° C to give the ionic polymer 3.3 gm NMR of 19F (DMSO) does not indicate any sulfonyl fluoride group. The dry hydrolyzed membrane was transferred to a sealed container while it was still hot and transported to a glove box having a positive pressure of dry nitrogen applied to it, where the membrane was removed from the sealed container and allowed that reaches room temperature, the membrane was cut in several sections Ions of 1.0 cm by 1.5 cm in size. Then a cooled membrane sample of 1.0 cm by 1.5 cm was rinsed in an excess of 1: 1 of EC and DMC mixture in a sealed glass jar for 1 hour at room temperature. The membrane was removed from the solvent bath, dried with a paper towel to remove excess solvent and tested using the four-point sample test described above. The absorption of the solvent was determined by the method described above. The absorption of the solvent was 25%. The conductivity was 2.16xl0 ~ 5 S / cm. It is noted that, with regard to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Claims (35)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. An olefinic composition represented by the formula: CF2 = CF (CF2CF2) nS02F characterized in that n = 1 to 5.
2. 2. The olefinic composition of according to claim 1, characterized in that n = 1.
3. 3. An ionizable olefinic composition represented by the formula: CF2 = CF (CF2CF2) nS03M characterized in that n = 5 and M is a univalent metal.
4. 4. The ionizable olefin composition according to claim 3, characterized in that n == 1 and M is lithium.
5. 5. A process for synthesizing the olefinic composition according to claim 1, characterized in that it comprises: (a) contacting CF2C1CFC1 (CF2CF2) nI, where n = 1 to 5, with Na2S204 and NaHC03 in a mixture of water and an aprotic polar solvent at a temperature in the range of room temperature to 110 ° C, to form CF2ClCFCl (CF2CF2) nS02Na; (b) contacting CF2C1CFC1 (CF2CF2) nS02Na with Cl2 in water or a mixture of water and a polar aprotic solvent at a temperature in the range of 0-200 ° C to form CF2C1CFC1 (CF2CF2) nS02Cl. (c) contacting CF2C1CFC1 (CF2CF2) nS02Cl with a univalent metal fluoride in an anhydrous polar aprotic solvent to form CF2C1CFC1 (CF2CF2) nS02F. (d) contacting CF2C1CFC1 (CF2CF2) nS02F with Zn in an alcohol or a mixture of acetic acid and alcohol to form CF2 = CF (CF2CF2) nS02F and (e) separating the product.
6. 6. The process according to claim 5, characterized in that n = 1.
7. 7. The process according to claim 5, characterized in that the polar aprotic solvent is selected from the group consisting of acetonitrile, dimethylformamide (DMF), tetrahydrofuran ( THF), dimethylsulfoxide (DMSO) and dimethyl acetamide (DMAC).
8. 8. A polymer characterized in that it comprises 0.1 to 50 mol% of monomer units represented by the formula: -CF, -CF- "I (CF2CF2)" S02 where n = 1 to 5, X is F u -OM where M is a univalent metal or hydrogen.
9. 9. The polymer according to claim 8, characterized in that n = l and X is F u -OLi.
10. The polymer according to claim 8, characterized in that it also comprises monomer units selected from the group consisting of ethylene, propylene, tetrafluoroethylene (TFE), hexafluoro-propylene (HFP), chlorotrifluoroethylene (CTFE), trifluoroethylene, vinylidene fluoride ( VF2), vinyl fluoride and mixtures thereof.
11. The polymer according to claim 8, characterized in that it also comprises monomeric units of ethylene or vinylidene fluoride.
12. The polymer according to claim 8, characterized in that it is a terpolymer comprising the combinations of monomer units selected from the group consisting of VF2 and HFP, VF2 and CTFE, TFE and ethylene, VF2 and TFE and VF2 and trifluoroethylene.
13. The polymer according to claim 8, characterized in that it is a terpolymer comprising the combinations of monomer units selected from the group consisting of VF2 and HFP, TFE and E and CTFE and E.
14. 14. The polymer according to the claim 8, characterized in that it also comprises monomer units of vinylidene fluoride.
15. 15. An ionomer characterized in that it comprises monomer units of vinylidene fluoride and 0.1 to 50% in mol of monomer units represented by the formula: -CF2-CF-I (CF2) p-OCF2CF2S03M wherein p is 1 to 10 and M is a metal univalent.
16. 16. The ionomer according to claim 15, characterized in that p = 1 and M is lithium.
17. 17. A process for forming an ionizable composition, characterized in that it comprises contacting at a temperature in the range of 0-85 ° C a composition comprising the functional group - (CF2CF2) n-S02F wherein n is 1 to 5 with a solution of an alkali metal salt, the pH of the solution is not greater than 13, for a period of time sufficient to obtain the desired degree of conversion to the alkali metal sulfonate form of the polymer.
18. 18. The process according to claim 17, characterized in that the composition further comprises a polymer having monomer units of vinylidene fluoride.
19. 19. An ionically conductive composition characterized in that it comprises the ionomer according to claim 15 and a liquid imbibed therein.
20. 20. The ionically conductive composition according to claim 19, characterized in that p = 1 and M is lithium.
21. 21. An ionically conductive composition characterized in that it comprises the polymer according to claim 8, wherein X is -OM and a liquid imbibed therein.
22. 22. The ionically conductive composition according to claim 21, characterized in that the polymer further comprises monomer units of vinylidene fluoride.
23. 23. An ionically conductive composition characterized in that it comprises the ionizable olefin composition according to claim 3 and a liquid.
24. 24. The ionically conductive composition according to claim 21 or claim 23, characterized in that M is lithium and n = 1.
25. 25. The ionically conductive composition according to claim 19, claim 21 or claim 23, characterized in that the Liquid is an aprotic solvent.
26. 26. The ionically conductive composition according to claim 25, characterized in that the aprotic solvent is selected from the group consisting of an aprotic solvent selected from the group consisting of dimethyl sulfoxide, ethylene carbonate, propylene carbonate, dimethoxyethane, gamma-butyrolactone, mixtures thereof and mixtures thereof with methyl carbonate.
27. 27. The ionically conductive composition according to claim 26, characterized in that the aprotic solvent is a mixture of ethylene carbonate and dimethyl carbonate.
28. 28. An electrode characterized in that it comprises at least one active electrode material and the polymer according to claim 8, wherein X is -OM.
29. 29. The electrode according to claim 28, characterized in that n = 1 and M is lithium.
30. 30. An electrode characterized in that it comprises at least one active electrode material and the ionomer according to claim 15.
31. 31. The electrode according to claim 30, characterized in that p = 1 and M is lithium.
32. 32. An electrochemical cell characterized in that it comprises a positive electrode, a negative electrode, a separator disposed between the positive and negative electrodes and means for connecting the cell to an external load or source, wherein at least one of the group consisting of the separator , the cathode and the anode comprises the polymer according to claim 8, wherein X is -OM.
33. 33. The electrochemical cell according to claim 32, characterized in that n = 1 and M is lithium.
34. 34. An electrochemical cell characterized in that it comprises a positive electrode, a negative electrode, a separator disposed between the positive and negative electrodes and means for connecting the cell to an external load or source, wherein at least one of the group consisting of the separator , the cathode and the anode comprises the ionomer according to claim 15.
35. 35. The electrochemical cell according to claim 34, characterized in that p = 1 and M is lithium.