MXPA00007297A - Fluorinated ionomers and their uses - Google Patents

Abstract

This invention concerns substantially fluorinated, but not perfluorinated, ionomers consisting of a polyethylene backbone having pendant groups of fluoroalkoxy sulfonic acids and metal salts thereof. Such ionomers are useful for electrochemical applications.

Description

FLUORITE IONOMERS AND THEIR USES FIELD OF THE INVENTION This invention concerns ionomers comprising substantially one fluorinated, but not perfluorinated, polyethylene backbone having dangling groups of fluoroalkoxysulfonic acids and the metal salts thereof, and with the uses of the ionomers in electromechanical applications such as batteries, cells fuel, electrolysis cells., ion exchange membranes, sensors, electrochemical capacitors, and modified electrodes.

BACKGROUND OF THE INVENTION Copolymers of vinylidene fluoride (VDF) with vinylalkoxysulfonyl halides are known in the art.

It is presented in Ezzell et al. (U.S. 4,840,525) encompasses copolymers of VDF with the vinyl ethoxy sulfonyl fluorides containing another linkage.

REF .: 121534 A process for the emulsion polymerization of tetrafluoroethylene (TFE) with the comonomer of vini.l ethoxy is exposed.

Banerjee et. (U.S. 5,672,438) discloses the VDF copolymers with vinyl alkoxy sulfonyl fluorides containing more than one bond.

Connolly et al. (U.S. 3,282,875) discloses the VDF terpolymer with perfluorosulfonyl fluoroethoxy propyl vinyl ether (PSEPVE) and hexafluoropropylene (HFP). They amply show an emulsion polymerization process which is applicable to the copolymerization of vinyl ethers with any ethylenically unsaturated comonomer, with greater applicability for the fluorinated monomers.

Barnes et al (U.S. 5,595,676) "substantially fluorinated" copolymers of monomer containing cation exchange groups of vinyl ether with a "substantially fluorinated" alkene. The copolymer is produced by the controlled addition of the alkene in the emulsion polymerization, followed by hydrolysis in NaOH. PSEPVE / TFE copolymers are exemplified.

Hietala et al. J. Mater. Chem. Volume 7 pages 721-726, 1997, discloses a porous polyvinylidene fluoride wherein the styrene is grafted upon exposure of the PVDF to the radiation. The functionality of styrene is subsequently functionalized by sulfonic acid by exposure of the polymer with chlorosulfonic acid. The resulting acid polymer, in combination with water, provides a membrane that drives the protons.

The formation of acidic ionomers and copolymers by hydrolysis of the functionality of the sulfonyl fluoride in the TFE copolymers and the fluoro alkoxy sulfonyl fluorides are well known in the art. The art shows the exposure of the copolymer strongly basic conditions.

See, for example, Ezzell et al. U.S. 4,940,525, where 25% by weight of NaOH (aq.) Was used for 16 hours at 80-90 ° C; Banerjee et al. U.S. 5,672,438, where 25% by weight of NaOH was used for 16 hours at 90 ° C, or, in the alternative, an aqueous solution of 6-20% alkali metal hydroxide and 5-40% polar organic liquid (per example, DMSO) for 5 minutes at 50-100 ° C; Ezzell et al. U.S. 4,358,545 where 0.05 N of NaOH was used for 30 minutes at 50 ° C; Ezzell et al. U.S. 4,330,654, where 95% ethanol was used at the boiling point followed by the addition of equal volume of 30% NaOH (aq) with continuous heating for 1 hour; Marshall et al. EP 0345964 Al, where 32% by weight NaOH (aq.) And methanol were used for 16 hours at 70 ° C, or, in an alternative, an aqueous solution of 11% by weight KOH and 30% DMSO in Weight for 1 hour at 90 ° C; and Barnes et al. U.S. 5,595,676, where 20% by weight NaOH (aq.) Was used for 17 hours at 90 ° C.

Due to its high dielectric count, high electrochemical stability, and desirable swelling properties, polyvinylidene fluoride is known in the art of lithium batteries as a highly desirable material for use as a separating membrane. For example Gozdz et al. (U.S. 5,418,091) discloses homopolymer and porous PVDF copolymers containing solutions of lithium salts in aprotic solvents useful as separators in lithium batteries.

Porous membranes of the type described by Gozdz, however, lead back the cation and the anion and through the separator, and therefore are subject to concentration polarization during use, which degrades the development of the battery when it is used. . The simple ionic conductive polymer membranes called thus, where the ionic salt- adhere to the main chain of the polymer, by means of this the cation or the anion is immobilized, offering a solution to the problem of polarization of concentration, and they are known in art. Particularly well known as a single ion conductive polymer is Nafion® Perfluoroionomer Resin and Membranes available from DuPont, Wilmington, Delaware. Naphion in a TFE 'copolymer and perfluoro (3,6-dioxa-4-methyl-7-octensulfonyl) fluoride which has been hydrolyzed by treatment with an alkali metal hydroxide according to the art techniques as described above.

It is also known in the art, and it will be shown at once, that the homopolymers and copolymers of PVDF are subjected to the attack of strong bases such as the alkali metal hydroxides shown in the art cited above. Of particular importance is that the attack of the basic nucleophiles in a copolymer of VDF and perfluorovinyl ethers results from the removal of the vinyl ether radical from the polymer, see W.W. Schmiegel in Die Angewndte Makromolekulare Chemie, 76/77 pp 39ff, 1979. Since the highly preferred polymer species shown in the art, and exemplified by Nafion and similar products of DuPont, by imparting ionomeric character to various polymers is a vinyl ether terminated by a sulfonyl halide functionality, the attack sensitivity of the VDF copolymer base formed therewith has prevented the development of a single ion conductive ionomer based on VDF. There is simply no means that shows in the art of making the ionomer.

Patent EP-A-0779335 discloses the paint formulations comprising aqueous dispersions of vinylidene fluoride copolymers and ca. 0.1% by weight of the reaction medium of a reactive emulsifying agent comprising sulfonic acids of perfluoro vinyl ether and sulfonate salts.

FR-A-2499594 discloses the compositions formed by grafting the sulfonyl fluoride monomer preferred in Applicant's invention to a pre-existing polymer chain having vinylidene fluoride monomer units. The resulting polymer in D2 has an adhered group of formula: - CF2CF2? C F2C F (CF3) OC F2CF2 S02 F, EP-A-0753534 describes ionomers formed from copolymers of tetrafluoroethylene and sulfonic acids and sulfonates of perfluorovinyl ether.

Patent EP-A-0053455 discloses the formation of ionomers by hydrolyzing the sulfonyl fluorides of perfluorovinyl ether under strongly basic conditions.

BRIEF DESCRIPTION OF THE INVENTION The present invention solves this problem that has remained for a long time. This invention provides an ionomer comprising the units of the VDF monomer and a perfluoroalkenyl monomer having an attached ionic group represented by the formula: - (0-CF2CFR) aO-CF2 (CFR ') bS03 ~ M + wherein R and R 'are independently selected from F, Cl, or a perfluorinated alkyl group having from 1 to 10 carbon atoms, a = 0.1 or 2, b = 0 to 6, and M is H or a metal univalent.

The present invention also provides a functionalized olefin of the formula CF2 = CF- (0-CF2CFR) aO-CF2 (CFR ') bS03"M + wherein R and R 'are independently selected from F, Cl, or a perfluorinated alkyl group having from 1 to 10 carbon atoms, a = 0.1, 2, b = 0 to 6, and M is a univalent metal.

The present invention further provides a process for forming an ionomer, the process comprising contacting a polymer comprising units of VDF monomers and a perfluoroalkenyl monomer having an adhered group of the formula - (0-CF2CFR) aO-CF2 (CFR ') bS03F wherein R and R 'are independently selected from F, Cl, or a perfluorinated alkyl group having from 1 to 10 carbon atoms, a = 0, 1 or 2, b = 0 a 6, with a suspension or solution of an alkali metal salt 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 also provides an ionically conductive composition comprising the polymer of the invention and a liquid absorbed therein.

The present invention further provides an electrode comprising at least one electrode of active material, the ionomer polymer of the present invention mixed therewith, and a liquid absorbed therein.

The present invention further comprises an electrochemical cell comprising a positive electrode, a negative electrode, a separator placed between the positive and negative electrodes, and a means for connecting the cell to an external load or source wherein at least one group consists of the separator, the cathode, and the anode, comprises the conductive composition of the invention.

DETAILED DESCRIPTION OF THE INVENTION For the purposes of the description of the present invention, the generic term "ionomer" will be taken to encompass the metal sulfonate and sulfonic acid forms of the polymer of the invention.

In a surprising aspect of the present invention, a non-destructive method for hydrolyzing sulfonyl fluoride in a polymer comprising VDF monomer units and a perfluoroalkenyl monomer having a group attached to the formula has been discovered. - (0-CF2CFR) a0-CF2 (CFR ') bS02F to form the ionomer of the invention the ionomer is a polymer comprising VDF monomer units and an ionic perfluoroalkenyl monomer having an adhered group of formula - (0-CF2CFR) aO-CF2 (CFR ') bS03 ~ M + wherein R and R' are independently selected from F, Cl, or a perfluorinated alkyl group having from 1 to 10 carbon atoms, a = 0.1 or 2, b = 0 to 6, and M is H or a univalent metal. Preferably, R is trifluoromethyl, R 'is F, a = 0 or b = 1, and M is H or an alkali metal. More preferably, a = 1 and M is Li.

In another surprising aspect of the present invention, the same non-destructive method is applicable to hydrolyze a functionalized olefin of formula CF2 = CF- (0-CF2CFR) aO-CF2 (CFR '.) BS02F I) to form the ionic olefin of the present invention, the ionic olefin has the formula CF2 = CF- (0-CF2CFR) a0-CF2 (CFR ') bS03 ~ M' (ID wherein R and R 'are independently selected from F, Cl, or a fluorinated alkyl group, preferably perfluorinated, having from 1 to 10 carbon atoms, a = 0, 1 or 2, b = 0 to 6.

Preferably, R is trifluoromethyl, R 'is F, a = l or b = l, and M is a univalent metal.

The ionomer of the invention can first be formed by copolymerizing a non-ionic monomer (I) with VDF followed by hydrolysis to form the ionomer of the invention, or alternatively, by first hydrolyzing the monomer (I) to form the ionic monomer of the invention (II), followed by the polymerization with VDF to form the ionomer of the invention. The process of polymerizing first followed by hydrolysis is preferred for operational simplicity.

A preferred hydrolysis process of the invention comprises contacting the monomer or polymer containing the sulfonyl fluoride with a mixture of alkali metal carbonate and methanol (optionally containing another solvent such as dimethyl carbonate), in a range of AC. 0-85 ° C, preferably at room temperature at 65 ° C for a sufficient time to convert the desired percentage of sulfonyl fluoride to the sulfonate of the related metal. The alkali metal carbonate is selected to provide the desired cation for the intended application. Suitable alkali metal carbonates include Li 2 CO 3, Na 2 CO 3 and K 2 CO 3, with Li 2 CO 3 the most preferred.

Generally preferred are the mildest possible hydrolysis conditions consistent with the time conversion of the sulfonyl fluoride to the desired ionic form. The severe hydrolysis conditions shown in the art of the hydrolysis of sulfonyl fluoride to sulfonate causes the degradation of the copolymer containing VDF. The degree of conversion can be conveniently recorded by the disappearance of the characteristic infrared absorption band of the fluoride sulfonyl group around 1470 cm "1. Alternatively, 19 F NMR spectroscopy can be used as described in the examples.

The ionomers of the invention include copolymer compositions wherein the ionic monomer unit is present in the ionomer of the invention with a concentration range from 1 to 50 mol%, preferably 2-20 mol%.

Preferred ionomers comprise 80-98 mol% of VDF monomer units and 2-20 mol% of perfluoro (3,6-dioxa-4-methyl-7-octen sulfonate lithium).

Other cationic forms of the ion exchange membrane can be made using ion exchange procedures 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 aqueous acid.

Silver-copper sulfonate ionomers can be made by ion exchange with alkali metal sulfonate which forms 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 for partial cation exchange. 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 copper chloride.

In several applications, the ionomer is preferably formed in a film or sheet. The ionomer films can be formed according to the processes known in the art. In one embodiment, the sulphonyl fluoride precursor thermoplastic is extrusion molded into a cooled surface such as a rotating drum or roll, where it is subjected to hydrolysis according to the process described above. In a second embodiment, the sulfonyl fluoride precursor was dissolved in a solvent, in the molding on a flat surface such as a glass plate using a doctor blade or other apparatus known in the art to help deposit the films in a substrate, and the resulting film subject to hydrolysis. In a third embodiment, the sulfonyl fluoride copolymer resin was subjected to hydrolysis by dissolution or suspension in a hydrolyzing medium, followed by optional addition of a co-solvent and filtration or centrifugation of the resulting medium, and finally molding with solvent of the ionomer solution on a substrate using a doctor blade or other apparatus known in the art to assist in the deposition of the films on a substrate. In a fourth embodiment, the ionic comonomer (II) and VDF are copolymerized as described below, preferably in water, and the resulting polymer deposited on a substrate utilizes a doctor blade or other device known in the art.

It is found in the practice of the present invention that a thin film of the copolymer containing the sulfonyl fluoride exhibits a tendency to dissolve during hydrolysis when the concentration of the sulfonyl fluoride radical exceeds about 5 mol%. Therefore the purpose of the process that forms the film achieving better control, is preferably found by suspending the precursor polymer containing nonionic sulfonyl fluoride in a solvent or combination of solvents, such as methanol, dimethyl carbamate, or mixtures of these , also those containing the hydrolyzing agent, preferably Li2C03 by means of the hydrolysis of the polymer in solution. The polymer thus hydrolyzed is then molded as a film from the solution.

The ionomer of the present invention, however formed, exhibits a low level of ionic conductivity in the dry state, at room temperature, typically ca. 10 ~ 6 S / cm. It can be combined with a liquid to achieve high levels of ionic conductivity. Depending on the requirements of the application, the ionomer will be in acid form or in salt form, the metal in particular is also determined by the application. The liquid used with this in the same way will dictate the application. In general terms, it has been found in the practice of the invention that the conductivity of the liquid-containing ionomer increases with a current increase in% by weight, increasing the dielectric constant and increasing the Lewis basicity of the liquid, while it has been observed that the conductivity decreases when increasing the viscosity and increasing the molecular weight of the liquid used. Of course, other considerations also come into play. For example, the exclusive solubility of the ionomer in the liquid may be undesirable. 0, the liquid can be electrochemically unstable for intentional use.

A particularly preferred embodiment comprises the lithium ionomer combined with aprotic solvents, preferably organic carbonates, which are useful in lithium batteries. This is in lithium batteries where the particularly useful attributes of the ionomer of the invention are particularly remarkable. A powerful solvent takes on characteristics of VDF polymers resulting in highly desirable ionic conductivity in the membrane that is ignited by the solvent. In addition, VDF imparts highly desirable electrochemical stability in the lithium battery environment.

It was found in the practice of the invention that the ionomer of the invention containing at least 50% of VDF, more preferably at least 80% of VDF, can become excessively plasticized by the solvents absorbed inside it, with lost detachment of the physical integrity of the membrane. In some applications, it may be desirable to improve the properties of the membrane inflamed with the solvent. The means available for improving the mechanical properties include: 1) incorporation into the polymer by means known in the art, and following the synthetic method described below, a third nonionic monomer that is less sensitive to the solvent; 2) the formation by means of known means of a mixture of polymer with a nonionic polymer that is less sensitive to the solvent, 3) mixing by means of known means of the ionomer of the invention with an inert filler; 4) the mixing of different ionic copolymer compositions; and 5) the link.

Suitable third monomers include tetrafluoroethylene, chlorotrifluoroethylene, ethylene, hexafluoropropylene, trifluoroethylene, vinyl fluoride, chloride. of vinyl, vinylidene chloride, perfluoroalkylvinyl ethers of formula CF2 = CFORf where Rf = CF3, C2F5 or C3F6. Preferred thermonomers include tetrafluoroethylene, hexafluoropropylene, ethylene, and perfluoroalkyl vinyl ethers. The thermonomers are preferably present in the polymer at a concentration of up to 30 mol%.

Polymers suitable for mixing with ionomers of the invention include poly (tetrafluoroethylene) and copolymers thereof with hexafluoropropylene or perfluoroalkyl vinyl ethers, vinylidene fluoride homopolymers and a copolymer thereof with hexafluoropropylene, polymethyl methacrylate, polyethylene oxide, and poly ( vinyl chloride). A preferred composition comprises 25 to 50% by weight of the PVDF homopolymer • mixed with the VDF ionomer of the present invention. These materials are easily mixed with 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. Small and large surface area particles smaller than 1.0 micron in diameter are desired, such are available for a preferred grade of Si02 under the trademark Cab-o-sil® TS-530 silica. Charges of up to 50% by weight of the filler are preferred.

The relatively high solubility of the ionomers of the present invention and their sulfonyl fluoride precursors provide a benefit in case of processing during the manufacture of the compounds of a battery but can be problematic during the final assembly of the product of the desired battery. In a preferred embodiment of the battery of the present invention, a battery of one or more electrochemical cells formed by the laminate is formed together with a film forming the anode, cathode and separating compositions of the present invention, all have been rigorously 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 the most preferred. The organic carbonates will not only inflate the ionomeric polymer, but also dissolve the polymer depending on its composition, the main determining factor is the degree of crystallinity, which in turn is related to the concentration of the ionic comonomer in the polymer. The challenge in inflaming the ionomer with solvent while minimizing polymer dissolution.

One means to achieve the necessary balance is the use of methods described above to improve the physical integrity of the solvent-containing ionomer. Another method comprises dissolving the ionomer in the preferred organic carbonate solvents, followed by introducing the resulting solution into the pores of an inert porous polymer support such as the porous polypropylene Celgard®, available from Hoechst-Celanese, or microporous PTFE. Gore-Tex, available from WL Gore Associates, Newark, DE.

For the practical, environmentally sound, low-cost manufacture of the components of the electrochemical cells, fusion processing is widely preferred with the solution processing shown in the art. It is therefore particularly surprising that the ionomers of the present invention are melt processed. Since ionomers that are melt processed such as Surlyn® ionomer resin, available from DuPont, have been widely known in the art, these ionomers are of very low electrical conductivity and are not suitable for use in lithium batteries or other applications. electrochemical The most highly conductive ionomers known in the art are suitable for use in electrochemical applications, since thermoplastics in the strict sense, exhibit prohibited high melt viscosities leaving the rules of conventional fusion processing methods to form them into articles trained In general, the temperatures required for the melt processing exceed the decomposition temperatures of the ionomers.

Since this is also known in the art to combine high viscosity polymers with solvents generally known as plasticizers in order to reduce the melt viscosity and aid the melting process, it was found in practice that the highly conductive ionomers in the art do not exhibit the necessary reduction in melt viscosity even with large solvent loads suitable for use in electrochemical applications. In addition, excessively high solvent loads have been identified with a degradation in the electrochemical development, and therefore undesirable.

In contrast to the ionomers of the art, the ionomer of the present invention in combination with 50-60% by weight, preferably 50-200% by weight, of solvents is suitable for use in electrochemistry, particularly lithium battery, applications They exhibit good fusion processing without degradation of optimal battery development.

Since it is not limited to this, it is believed that the suitable solvents contain donor atoms, a pair of electrons that dissolve the dipoles -CH2CF2- in the polymer backbone - is the key to effective plasticization. In art ionomers suitable for electrochemical applications, the polymer backbones do not exhibit sufficient polarity to allow the formation of solvates within them.

Preferred solvents include those useful for battery applications, such as organic carbonates, lactones, sulfones, etc., more preferably those with boiling points higher than the melting point of the ionomer alone. In the absence of solvent addition, the ionomers of the invention usually exhibit sufficiently high melt viscosity that the flow of the polymer is insufficient under practical conditions. When the compound fused with uniform compositions results in exhibiting substantially reduced viscosity to allow melt processing at acceptable temperatures, and simultaneously providing adequate mechanical strength and hardness for the use of the final application.

The preferred electrode of the invention comprises a mixture of one or more electrode-active materials in particular form, the ionomer of the invention, at least one electron-conducting additive, and at least one organic carbonate. Examples of active materials of the anode include, but are not limited to, carbon (graphite, coke, mesocarbons, polyacenes, and the like) and carbon intercalated with lithium, lithium metal nitrides such as Li2.6Co0.4N, oxides of tin, metallic lithium and lithium alloys, such as lithium alloys with aluminum, tin, magnesium, mercury, manganese, iron and zinc. The lithium intercalation anodes using carbon are preferred. Useful cathode active materials include, but are not limited to, oxides and sulfides. of transition metals, oxides and sulfides of transition metals with lithium, and organosulforated compounds. Examples of these are cobalt oxides, manganese oxides, molybdenum oxides, vanadium oxides, titanium sulfides, molybdenum and niobium, oxides with lithium such as manganese oxides with lithium as the main compound Li1 + xMn2-? 04, oxides manganese with lithium as the main compound with chromium absorbed LixCryMnz04, LiCo02, LiNi02, LiNixC _ x02 where x is 0 < x < 1, with a preferred arrangement of 0.5 < x < 0.95, LiCoV04, and mixtures of these. LiNixC γ-x02 is preferred. A highly preferred conductive electron that aids is black carbon, preferably Super P black carbon, available by 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 compounds in a common solvent and mixing together with the black carbon particles and the active particles of the electrode. For the cathodes the active material of the electrode is LiNi? Co1_x02 where 0 < x < 1, while for the anodes the active material of the preferred electrode are graphitized mesocarbon microbeads. For example, an electrode of the preferred lithium battery of the invention can be manufactured by dissolving the ionomer of the invention in a mixture of acetone and dimethylformamide, followed by the addition of particles of active material from the electrode and black carbon, followed by deposition. of a film on a substrate and drying. The preferred resultant electrode will comprise the active material of the electrode, conductive black carbon, and the ionomer of the invention, wherein, preferably, the weight ratio of the ionomer to the active material of the electrode is between 0.05 and 0.8 and the weight ratio of Black carbon with the active material of the electrode is between 0.01 and 0.2. More preferably the weight ratio of the ionomer to the active material of the electrode is between 0.1 and 0.25 and the weight ratio of black carbon to the active material of the electrode is between 0.02 and 0.1. This electrode can then be molded from the solution in a suitable support such as a glass plate or a common metal collector sheet, and formed into a film using techniques well known in the art. The electrode film thus produced can then be incorporated into a structure of the muti-layer electrochemical cell by means of lamination, as described below.

It may be desirable to incorporate in the electrode composition of the additional polymers of the invention or solvents for this purpose by employing the linkage of the compounds thereof, or to provide improved structural integrity of an article made therefrom. Particularly a preferred additional material is the PVDF homopolymer, which can be incorporated simply by dissolving the polymer in the same solution from which the electrode was formed, as described above.

In an alternate process, the dispersion of the active material of the electrode and the optional black carbon and other adjuvants can first be molded on a surface followed by the addition of the ionomer of the invention to the organic carbonate solution.

The invention is further described in the following specific embodiments.

EXAMPLES For the purposes of this invention, the term "conductivity" used herein refers specifically to the conductive ionic activity as determined using the so-called four-point test technique described in the 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 mentioned as described is applied to the membranes of the aqueous electrolyte. The method was modified for purposes of obtaining the measurements reported here for non-aqueous solvents by placing the described apparatus in a sealed glovebox purged with dry nitrogen in order to minimize any exposure to water. The method was also modified by substituting parallel linear tests running the full width of the test specimen at the test points used in the published method.

A film of 1.0 cm by 1.5 cm was dried and placed inside the conductivity cell. The impedance of the cell in the range of 10 Hz to 100,000 Hz was determined, and the value with zero phase angle in the higher frequency range (usually 500-5000 Hz) was attributed to the resistance of the bulk sample in Ohms . The value of the initial resistance was then converted to conductivity in S / cm, using the cell constant and the film thickness.

The solvent occupied was determined from the equation % busy = (Ww - Wd) / Wd where Wd is the weight of the membrane before contact with the solvent and Ww is the weight of the membrane after contact with the solvent determined first after the removal of the membrane from the solvent and after drying using a paper napkin to remove the excess solvent on the surface.

All chemicals used as received unless otherwise specified.

Differential scanning calorimetry (DSC) was developed according to ASTM D4591, in a nitrogen atmosphere and at a heating rate of 20 ° C / minute, using a TA Instruments Model 2910. Thermogravimetric analysis was developed using a TA Instruments Model 2950 with a heating rate of 10 ° C / min in air unless otherwise indicated.

The 19 F NMR spectrum was recorded using a Bruker ADVANCE DRX 400 spectrometer. The 1 H NMR spectrum was recorded using a Bruker ADVANCE DRX 500 spectrometer.

The intrinsic viscosity at 25 ° C in 1,2-dimethoxyethane was determined.

EXAMPLE 1 A 1 liter vertical stirred autoclave was charged with 500 ml of an aqueous solution of ammonium perfluorooctanate (7 g), available from 3 M Company, Minneapolis, MN, and PSEPVE (50.0 g, 0.112 mol). The PSEPVE was prepared in a manner described in D.J. Connally and W.F. Greshman, U.S. 3,282,875 (1966). The vessel was closed, pressurized twice at 100 psi nitrogen and vented, cooled to about 5 ° C and evacuated. Vinylidene fluoride (50.0 g, 0.78 mol) was added, and stirred (750 r.p.m.) the contents were heated to 60 ° C. A solution of 0.40 g of potassium persulfate in 20 ml of distilled water was added during a 20 minute interval. Pressure was reduced from 400 psi to 5 psi in 2 hours. The polymer was isolated by freeze / thaw coagulation. After washing with distilled water several times, the polymer sponge was cut into several pieces, frozen in liquid nitrogen, added to a mixer to produce a crumb of the polymer that was washed with additional portions of water. 95.5 g of white polymer was obtained after drying at 50 ° C under vacuum of 10 millitorr. The DSC was washed Tg = -23 ° C and at a maximum of a broad melting transition at 125 ° C (8.7 J / g). The TGA, developed under nitrogen showed at the beginning of the weight loss at ca. 250 ° C, with ca. 1% loss up to ca. 370 ° C. The intrinsic viscosity was 0.72 dl / g. The composition was found to be 87 mol% VDF and 13 mol% PSEPVE, as determined by a combination of 1 H and 19 F NMR. The NMR results were lE NMR (THF-d8): 3.3-2.9 (the flat surface of the lower field), 2.9-2.7 (main spectral line), 2.6 and 2.3 (minor spectral lines). NMR 19F (THF-d8) signals characterized to -45.4 (FS02), -78 to -80 (m's, OCF2 and CF3), -90 to -95 (m, CH2CF2), -110 to -123 (series of m, for minor CH2CF2 and CF2S), -144 (CF).

A sample of 8.9 g of PSEPVE / VF2 copolymer (ca 10 m equivalent of adhered sulfonyl fluoride) was suspended in methanol (50 mL), treated with lithium carbonate (0.81 g, 11 m equivalent C03), and stirred at 25 ° C. After 3 hr, another 50 ml of methanol was added and the mixture was stirred for 18 hr. The mixture was filtered under pressure through glass fiber paper. A portion of the methanol solution was used to mold films to test the conductivity and the remainder was evaporated to dryness under reduced pressure. 19F NMR (THF- d8) only showed a signal of residual FS02 radicals (conversion> 99%), the main signals at -76 to -82, -96.6, -93.1 and -95.3, - 108 to -112 and series of 'sa -113.6, -115.9, -117.5, -122 to -124, and -144 to -145 with integration -according to 13% mol incorporated with the lithium sulphate form of PSEPVE. I.V. = 0.73 dl / g.

EXAMPLE 2 A film of ca. 80 micrometers thick was molded from a methanol solution of Example 1, by spraying an aliquot of ca. of 3 mL at 25 ° C. After the slow evaporation of the solvent, the resulting film was then dried for a period of time in a vacuum oven.

The dried membrane was transferred to a dry container and transported in a box having a positive pressure of dry nitrogen applied therein, where the membrane was removed from the sealed container and allowed to reach room temperature. The membrane was then cut into several sections 1.0 cm by 1.5 cm in size.

Using a micropipette, 20 microliters of propylene carbonate (99%, Aldrich Chemical Co., Inc., Mileaukee, Wl) was deposited on a surface of the membrane sample at room temperature. Conductivity was measured after 10 minutes of solvent exposure, was 3.74 x 10 ~ 4 S / cm.

EXAMPLE 3 Another 1.0 cm by 1.5 cm sample of the dry membrane of Example 2 was treated according to the method described here except that the 1: 1 by volume solvent mixture of ethylene carbonate (98%, Aldrich Cehmical Co., Inc. , Milwaukee, Wl) and dimethyl carbonate (99%, Alfa Aesar, Ward Hill, MA). The conductivity was found to be 6.78 x 10 ~ 4 S / cm.

EXAMPLE 4 A 1.0 cm by 1.5 cm sample of the dried membrane of Example 2 was treated according to the method described herein except that the solvent was distilled and the water was deionized. The conductivity was equal to 2.15 x 10 ~ 2 S / cm.

EXAMPLE 5 A mixture of 1 g of Li ionomer of Example 1 and 1 g of the poly (vinylidene fluoride) homopolymer prepared by aqueous dispersion polymerization was placed in a closed glass flask containing 60 ml of acetone. Warm heating was applied while the contents were agitated at dispersion speed. Once the polymers dissolved, the aliquots in solution were deposited on a glass surface to form films by slow evaporation of solvent. The resulting films were dried for 18 hr at 50 ° C in a vacuum oven.

The dried membrane was transferred to a closed container and transported to a box having a positive pressure of dry nitrogen applied to it, where the membrane was removed from the sealed container and allowed to reach room temperature.

A 1.0 cm by 1.5 cm sample was totally immersed in an excess propylene carbonate solvent in a sealed glass jar. After 1 hour, the membrane was removed from the solvent, dried, and the weight occupied and the conductivity was measured. The occupied weight was 267% and the conductivity was 4.95xl0 ~ 4 S / cm.

EXAMPLE 6 A 1.0 cm by 1.5 cm sample of the membrane of Example 5 was treated according to the method described herein except that the solvent was a mixture of 1: 1 by volume of ethylene carbonate and dimethyl carbonate. After one hour, the full weight was 150% and the conductivity was 6.60 x 10"4 S / cm.

COMPARATIVE EXAMPLE 1 A sample of 9.0 g of a nonionic copolymer was synthesized in a manner similar to that used to synthesize the polymer of Example 1 except that the initiator was a solution of 0.08 g of potassium persulfate in 20 ml of water. The NMR indicated a composition of 86.8 mol% of VDF and 13.2 mol% of PSEPVE. A sample of 9.0 g of the polymer thus synthesized was placed in a flask with 100 ml of methanol and 0.9 g of lithium carbonate. The suspension was stirred at room temperature under argon for 48 hours. Then 500 ml of THF were added and the solution was filtered through a small funnel. The filtered solution was then placed in a dialysis tube (Spectra / Por (R) Dialysis Membrane, MWCO = 3500) and performed the dialysis again with deionized water for 11 days. The contents of the dialysis tubes were emptied into the flask and stirred in water under vacuum. The collected polymer was vacuum treated at 50 ° C. The composition of the polymer was found to be 86.8 mol% of VDF and 13.2 mol% of PSEPVE by a combination of NMR aH and 19F.

The films were molded by dissolving 0.58 g of polymer in a minimum amount of acetone and emptying the solution in PFA petri dishes. The solvent was allowed to evaporate slowly to allow a film to be further dried in a recirculating nitrogen oven (Electric Hotpack Company, Inc., Model 633, Philadelphia, PA) at T = 100 ° C for 48 hours. Following drying, the membrane was immersed in an excess of 1. 0 M nitric acid (Reagent grade, MS Science, Gibbstown, NJ) and heated at T = 80 ° C for one hour. Following this procedure, the membrane was rinsed with deionized water for several hours. The membrane was cleaned and intact after this procedure.

A 1.0 cm by 1.5 cm section of this membrane sample was completely immersed in an excess of LiOH (98%, EM Science, Gibbstown, NJ), 1.0 molar in a mixture of 1: 1 by volume of water and DMSO (HPLC) grade, Burdick &Jackson, Muskegon, MI) mixed at T = 70 ° C for 1 hour. Upon reaching the temperature, this sample of the membrane visibly became blackened and quickly decomposed by means of the hydrolysis bath. After one hour, the membrane sample was fractured into several small pieces and completely blackened.

EXAMPLE 7 A 1 liter vertical stirred autoclave was charged with 500 ml of an aqueous solution of ammonium perfluorooctanate (7 g), and PSEPVE (25. Og, 0.056 mol). The vessel was closed, pressurized twice at 100 psi nitrogen and vented, cooled to about 5 ° C and evacuated. Vinylidene fluoride (50.Og, 0.78 mol) was added, and the contents were stirred (750 r.p.m.) and heated to 60 ° C. A solution of potassium persulfate (0.08 g in 20 ml) was added during a 10-minute interval. Pressure was reduced from 400 psi to 5 psi in 3 hours. The polymer was isolated by freeze / thaw coagulation and washed thoroughly with distilled water. After drying, 69.4 g of white polymer were obtained.

It exhibited DSC at Tg = -23 ° C and at a maximum of a wide fusion transition at 120 ° C (14.9 J / g). The TGA, developed under nitrogen showed at the beginning of the weight loss at ca. 370 ° C. The composition was found to be 91.6 mol% of VDF and 8.4 mol% of PSEPVE, as determined by a combination of 1 H and 19 F NMR. The NMR results were 1K NMR (acetone-dß): 3.6-2.6 (m), 2.4 (minor spectral line). NMR 19F (acetone-d6): +45.57 (s), -78.0 to -80.0 (m's, a = 2.968), -90.0 to -95.0 (m's, a = 8.646), -108 to -116 (series of m, a = 2,721), -121 to -127 (m's, a = 1,004), -143 to -144.0 (m, a = 0.499); the integration using internal CF signals and the combined CF3 + CF20 signals to set the PSEPVE response indicating 0.462 / F for PSEPVE, 5.03 / F for VDF. g (26.2 milliequivalents) of the copolymer thus produced were placed in suspension. 300 ml of methanol and treated with 2.13 g of LiC03.

The resulting mixture was stirred for 42 hours.

An aliquot was analyzed by means of 19 F NMR showing > 99% conversion of sulfonyl fluoride groups to lithium sulphonate radicals.

A 50 ml portion of the methanol suspension was treated with ca. 120 ml of acetone and the resulting polymer solution was filtered under pressure. The filtered solution was used a preparation of several film samples for a later test after the standard drying procedures. NMR 19F (acetone-d6): +45.6 (signal traces, a = lower detection limits), -77.0 to -83.0 (m's, a = 13.68), -88.0 to -100.0 (m's, a = 38.9), -108 to 118 (series of m, a = 10.78), -122 to 128 (m's, a = 4.86), -144 to 145.5 (m, a = 2.12); consistent with 91.6% mol of VDF, 8.4% mol Li- PSEPVE.

TGA showed a gradual loss of 3% by weight with ca. 250 ° C, followed by an initiation of weight loss at 275 ° C. The DSC characterized a maximum of a broad melting transition at 126 ° C.

COMPARATIVE EXAMPLE 2 A 3"by 3" sample of the Nafion® 117 perfluorinated ionomer membrane available from the DuPont Company, Wilmington DE, was exposed to an excess of LiOH (98%, EM Science, Gibbstown, NJ), 1.0 molar in a 1 mixture: 1 in volume of water and DMSO (HPLC grade, burdíck &; Jackson, Muskegon, MI) was mixed at T = 60 ° C for 2 hours, then the membrane was washed in distilled water for 2 hours at T = 80 ° C, and dried in a nitrogen recirculation oven (Electric Hotpack Company , Inc., Model 633, Philadelphia, PA) at 100 ° C for 96 hours.

The dried membrane was transferred to a sealed container while it remained warm and transported in a box having a positive pressure of dry nitrogen applied therein, where the membrane was removed from the sealed container and allowed to reach room temperature. The membrane was then cut into several sections of 1.0 cm by 1.5 cm in size.

A 1.0 cm by 1.5 cm sample of the cold membrane was soaked in excess propylene carbonate (99%, Aldrich Chemical Co., Inc., Milwaukee, Wl) in a sealed glass jar for 2 hours at room temperature. The membrane of the propylene carbonate bath was removed, dried with paper napkins to remove excess solvent. The conductivity was determined to be 2.16 x 10-5 S / cm.

EXAMPLE 9 The 0.5 g of the hydrolyzed Li2C03 ionomer prepared in the manner of Comparative Example 1 was dissolved in 15-20 ml of THF in a flask equipped with a stir bar. 0.1 g of Cab-o-sil® TS-530 was added to the solution and dispersed by agitation. The films were molded around PFA petri dishes (50 mm diameter). The solvent was allowed to evaporate to produce a film that was dried under vacuum for 48 hours at 100 ° C in a vacuum oven. The resulting film hardened and easily separated from the substrate. The film was hydrolyzed to the lithium ionomer by the method described herein. The conductivity was determined after soaking in distilled water, it was 7.02 x 10"3 S / cm.

EXAMPLE 10 A 500-ml 3-necked flat bottom flask equipped with a magnetic stir bar, 2 Seventh, and a water condenser in addition to a nitrogen source was charged with PSEPVE (98g, 0.22 mol) and methanol (200 mL). The solution was stirred and the lithium carbonate (16.2 g, 0.22 mol) was added in 3-portions. No exothermic activity was observed. The mixture was stirred 3 days at room temperature. The reaction mixture was centrifuged, then the creams were decanted and concentrated by vacuum distillation. The rigorous drying of the salt was carried out by placing it on a plate in a hot tube (80 ° C) with a flow of N2. The methanol content was 1.2 mol% (determined by 1H NMR in D20 with standard internal integration CH3COOH). Another sample was dried in a tube packed with 0.6% methanol content. The analytical data were consistent with the structure, Li03SCF2CF2OCF (CF3) CF2OCF-CF2. NMR 19F (D20) 5-81.1 (m, 2F), -18.5 (m, 3F), -86.3 (m, 2F), -116.0 (dd, 86.1, 65.4 Hz, IF), -119.0 (d, 7.6) Hz, 2F), -123.8 (ddm, 112.3, 86.1 Hz, 1F), -137.8 (ddm, 112.3, 65.4 Hz, 1F), -146.4. (m, 1F); FTIR (NaCl) 1780.6 (m), 1383.3 (w), 1309.0 (vs), 1168.2 (m).

EXAMPLE 11 A 1 liter vertical stirred autoclave was charged with 500 ml of an aqueous solution of the ionic olefin from Example 10 25.0g, 0.056 mol). The vessel was closed, pressurized twice at 100 psi nitrogen and vented, cooled to about 5 ° C and evacuated. Vinylidene fluoride (50.Og, 0.78 mol) was added, and the contents were stirred (750 r.p.m.) and heated to 60 ° C. A solution of potassium persulfate (0.08 g in 20 ml) was added during a 10 minute interval. Pressure was reduced from 400 psi to 5 psi in 8 hours. Evaporation of the water from the copolymer solution resulted in 54 g of white solid. It exhibited DSC (10 ° / min, N2) which exhibited a maximum of a wide fusion transition at 157 ° C (10.7 J / g). The TGA (10 ° / min, N2) showed at the beginning of the loss of 5% by weight (40-150 ° C attributed to the loss of water binding) and the onset of the weight loss at ca. 260 ° C. The "NMR"? (acetone-d6): 3.6-2.6 (m), 2.4 (minor spectral line). NMR 19F (acetone-d6): -78.0 to -80.0 (m's, a = 84.9), -90.0 to -95.0 (m's, a = 236.9), -108 to -116 (m series) and -121 to -127 (m's, combined a = 112.5), -144 to -145.0 (m, a = 15.1); the integration using internal CF signals and the combined CF3 + CF20 signals to set the Li-PSEPVE response indicating 13.6 / F for PSEPVE, 140.7 / F for VDF. Therefore,% mol VDF = 91.2%; % mol Li-PSEPVE = 8.8% and% weight VDF = 57.4%; % weight Li-PSEPVE = 42.6.

EXAMPLE 12 Next is a description of a separator and an electric cell using an ionomer of the invention in the electrolyte. Both the separator and the electrode can be considered porous structures absorbed with a liquid electrolyte, the electrolyte is a mixture of ionomer dissolved in liquid solvents based on carbonate.

The following lithiation / dialysis procedure is used for the example of the film filled with silica. A sample of the polymer of Example 1, a copolymer of 87 mol% of VF2 / 13 mol% of PSEPVE, was placed in a flask with 100 ml of methanol and 0.9 g of lithium carbonate. The suspension was allowed to stir at room temperature under argon for 48 hours. THF (500 ml) was added and the solution was filtered through a small funnel. The solution was then placed in dialysis tubes (Spectra / Por® Dialysis Membrane, MWCO = 3500 of VWR) and dialysis was performed against deionized water for 11 days. The contents of the dialysis tubes were emptied into the flask and the water removed under vacuum. The collected ionomer was then dried under vacuum at 50 ° C.

In a box filled with argon, an electrolyte solution was prepared using 200 mg of the ionomer (in lithium forms) dissolved in 2 ml of a 50:50 p: p mixture of ethylene carbonate and dimethyl carbonate. A microporous polyolefin separator (Celgard® 3501, Hoechst Celanese) was soaked in the electrolyte for 2 hours and gained 65% by weight. Its ionic conductivity, a 4-point test was measured, was 10"3 S / cm.

A cathode film was prepared by making a suspension containing 4 g of Li? .05Mn2O (particle size 50 m), 0.215 g of black carbon SP, 2.5 ml of 4% of EPDM in cyclohexane (a solution containing 4 g. g of Dupont Nordel® 3681 EPDM gum dissolved in 96 g of cyclohexane), and an additional 2.5 ml of cyclohexane. The ingredients were stirred together in a glass jar with glass beds for 15 minutes, and then the suspension was molded into the FEP film using a doctor blade with a bridge height of 10 mil. The solvent was allowed to evaporate at room temperature, giving the film with a coating with a weight of 21 mg / cm2. The cathode film was removed from the FEP base film, placed between the 5-mil Kapton® sheets, and this in turn was placed between 5mil brass sheets. This cathode package was then compressed between the steel rollers heated to 110 ° C and with a force of 2.8 pounds per inch of pressure width when using a laminator (Western Magnum XRL-14, El Segundo, CA). The cathodes of 13.6 mm diam. They were marked off the film, and dried under vacuum at 80 ° C for 30 min.

A cathode (31.2 mg, 13.6 mm diameter) and a microporous polyolefin spacer was stirred in the electrolyte solution for about two hours. They were assembled with an anode with lithium sheet with thickness of 320 um in a wedge cell of size 2325. The cell was charged with constant current at 0.5 mA with a voltage of 4.3 V, at this point the voltage remained constant until the low voltage drop to 0.05 mA. The capacity at the first charge was 3.81 mAh, which represents 131 mAh per g of the lithium manganese oxide cathode material. The cell was discharged with a 0.5 mA at a speed of 3.7 V, and then the constant voltage was maintained at 3.7 V until the discharge of the discharge current below 0.05 mA. The discharge capacity was 3.15 mAh. The cell was repeatedly charged and discharged in a similar manner around the 7th discharge capacity \ which is 2.96 mAh. The AC impedance of the cell was measured to be 98 ohm with a frequency of 0. 01Hz.

EXAMPLE 13 Preparation of a vinylidene fluoride copolymer and PSEPVE A copolymer of vinylidene fluoride and PSEPVE containing 3.5 mole% of PSEPVE was prepared and hydrolyzed according to the methods provided herein. The ionomers thus formed were found by differential scanning calorimetry (DSC) to exhibit a melting transition peak at 140.8 ° C with a latent heat of fusion of 20 J / g. A die-cast film was obtained in a hydraulic press operated at 200 ° C and a force piston >; 25,000 lb. At lower conditions did not result with acceptable films. However, after a 1.0 g sample of the above ionomer was melt blended at 125 ° C with an equal part of propylene carbonate, the clear, uniform, elastic mass formed with this was then pressed at 120 ° C with a force of piston less than 5,000 lb. in a uniform film. The DSC analysis showed a melting peak at 115 ° C with a latent heat of fusion of -18 J / g, and Tg at ca. 70 ° C.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (34)

1. An ionomer comprising the units of the VDF monomer and a perfluoroalkenyl monomer having an attached ionic group represented by the formula: - (0-CF2CFR) aO-CF2 (CFR ') bS03 ~ M + characterized in that R and R 'are independently selected from F, Cl, or a perfluorinated alkyl group having from 1 to 10 carbon atoms, a = 0, l, 2, b = 0 to 6, and M + is H + or a cation of univalent metal, wherein the molar concentration of the ionic adhered group in the ionomer is in the range of 1-50%.

2. The ionomer of Claim 1, characterized in that R is trifluoromethyl or F, R 'is F, a = 0 or 1, and b = 1.

3. The ionomer of Claim 1, characterized in that M + is an alkali metal cation.

4. The ionomer of Claim 2, characterized in that R is trifluoromethyl and a = 1.

5. The ionomer of Claim 3, characterized in that M + is a lithium cation.

6. The ionomer of Claim 1, characterized in that the molar concentration of the ionic adhered group in the ionomer is in the range of 2-20%.

7. The ionomer of Claim 1, characterized in that it is in the form of a film or sheet.

8. The ionomer of Claim 1, characterized in that it further comprises up to 30 mol% of one or more additional monomer units selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, ethylene, hexafluoropropylene, trifluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride , perfluoroalkylvinyl ethers of the formula CF2 = CFORf where Rf = CF3, C2F5 or C3F6.

9. The ionomer of Claim 8, characterized in that the additional monomer units are selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, ethylene, and perfluoroalkylvinyl ethers.

10. The ionomer of Claim 1, characterized in that it also comprises nonionic polymer mixed therewith.

11. The ionomer of Claim 10, characterized in that the nonionic polymer is selected from the group consisting of poly (tetrafluoroethylene) and copolymer thereof with hexafluoropropylene or perfluoroalkylvinyl ethers, poly (vinylidene fluoride) homopolymer and a copolymer thereof with hexafluoropropylene , polymethyl methacrylate, polyethylene oxide, and poly (vinyl chloride).

12. The ionomer of Claim 11, characterized in that poly (vinylidene fluoride) is mixed therewith, the polyvinylidene fluoride is present in the mixture at a concentration in the range of 25-50% by weight of the total.

13. The ionomer of Claim 1, characterized in that it also comprises the inorganic particles mixed with it.

14. The ionomer of Claim 13, characterized in that the inorganic particles are silica particles with an average particle size of less than 1.0 microns, the silica present in the mixture with up to 50% by weight of the total.

15. A functionalized olefin of formula CF2 = CF- (0-CF2CFR) aO-CF2 (CFR ') bS03"M + characterized in that R and R 'are independently selected from F, Cl, or a perfluorinated alkyl group having from 1 to 10 carbon atoms, a = 0.1 O 2, b = 0 to 6, and M is a univalent metal.

16. A process for forming an ionomer, characterized in that the process comprises contacting a polymer comprising VDF monomer units and a perfluoroalkenyl monomer having an adhered group of the formula - (0-CF2CFR) aO-CF2 (CFR ') bS03F wherein R and R 'are independently selected from F, Cl, or a perfluorinated alkyl group having from 1 to 10 carbon atoms, a = 0, 1 or 2, b = 0 a 6, with a suspension or solution of an alkali metal salt for a period of time sufficient to obtain the desired degree of conversion to the alkali metal sulfonate form of the polymer.

17. A process for forming an ionically functionalized olefin, characterized in that the process comprises contacting a functionalized olefin having the formula CF2 = CF- (0-CF2CFR) aO-CF2 (CFR ') bS03F wherein R and R 'are independently selected from F, Cl, or a perfluorinated alkyl group having from 1 to 10 carbon atoms, a = 0.1 O 2, b = 0 a 6, with a mixture of an alkali metal salt and a solvent for a period of time sufficient to obtain the desired degree of conversion to form the alkali metal sulfonate of the olefin.

18. An ionically conductive composition, characterized in that it comprises the ionomer of Claim 1, and a liquid absorbed therein.

19. An ionically conductive composition of Claim 18, characterized in that the liquid is a protic liquid.

20. An ionically conductive composition of Claim 19, characterized in that the liquid is water or methanol.

21. An ionically conductive composition of Claim 18, characterized in that the liquid is an aprotic liquid.

22. An ionically conductive composition of Claim 21, characterized in that the liquid is selected from the group consisting of organic carbonates and mixtures thereof.

23. An ionically conductive composition of Claim 22, characterized in that the liquid is a mixture of ethylene carbonate and at least one liquid selected from the group consisting of dimethyl carbonate, methyl ethyl carbonate and acetyl carbonate.

24. An ionically conductive composition of Claim 18, characterized in that R is trifluoromethyl, a = 1, M + is a lithium cation, the molar concentration of the ionic adhered group in the ionomer is in the range of 2-20%, and the liquid is Select from the group consisting of organic carbonates and mixtures of these.

25. An ionically conductive composition of Claim 18, characterized in that they are a form selected from the group consisting of a film, a sheet or gel.

26. An ionically conductive composition of Claim 25, characterized in that it further comprises a microporous electrically insulating polymer film or sheet within the micropores the gel is absorbed.

27. An electrode, characterized in that it comprises at least one active material of the electrode, the ionomeric polymer of Claim 1 mixed therewith, and a liquid absorbed therein.

28. The electrode of Claim 27, characterized in that R is trifluoromethyl, a = 1, M + is a lithium cation, the molar concentration of the ionic adhered group in the ionomer is in the range of 5-20%, and the liquid is selected from the group consisting of organic carbonates and mixtures thereof.

29. The electrode of Claim 27, characterized in that the weight ratio of the ionomer to the active material of the electrode is between 0.05 and 0.8 and the weight ratio of black carbon to the active material of the electrode is between 0.01 and 0.2.

30. An electrochemical cell which comprises a positive electrode, a negative electrode, a separator placed between the positive and negative electrodes, and a means for connecting the cell to an external load or source, wherein at least one group consists of the separator. , the cathode, and the anode, characterized in that it comprises the conductive composition of claim 19.

31. A process for forming shaped articles, characterized in that it combines the ionomer of Claim 1 with a solvent, melt and form a shaped article, and then cool the formed article.

32. The process of claim 31, characterized in that the solvent is an organic carbonate and wherein the solvent is incorporated at a concentration of 50% -200% by weight.

33. The ionomer of Claim 1, characterized in that it has a melting point of at least 150 degrees C.

34. A process for forming an ionomer, characterized in that it comprises polymerizing the ionically functionalized olefin of Claim 18 with vinylidene fluoride in an aqueous medium, wherein the olefin is at a concentration of about 1 to 50% in the medium.