TW201241013A - Ionomers and ionically conductive compositions for use as one or more electrode of a fuel cell - Google Patents

Abstract

This invention relates to solid polymer electrolyte materials for use in one or more electrode of a fuel cell. The solid polymer electrolyte materiais comprise one or more ionomer which comprises polymerized units of monomers A and monomers B, wherein monomers A are perfluoro dioxole or perfluoro dioxolane monomers, and the monomers B are functionalized perfluoro olefins having fluoroalkyl sulfonyl, fluoroalkyl sulfonate or fluoroalkyl sulfonic acid pendant groups, CF2=CF(O)[CF2]nSO2X.

Description

201241013 VI. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a solid polymer electrolyte material used as one or more electrodes in a fuel cell. The solid polymer electrolyte material comprises one or more ionic polymers comprising polymerized units of monomer A and monomer B, wherein monomer A疋 perfluorodioxole or perfluorodioxolane And monomer B is a functionalized perfluoroolefin having a fluoroalkylsulfonyl group, a fluoroalkyl sulfonate or a pendant fluoroalkylsulfonic acid group CF2=CF(〇)[CF2]nS〇2X. [Prior Art] In the related art, it has been known for a long time to form an ion conductive film and a gel from an organic polymer containing an ion side group. This polymer is called an ionic polymer. A particularly known ionic polymer membrane that is widely used commercially is DuPont's Nafion® membrane. It is formed by copolymerization of tetrafluoroethylene (TFE) with perfluoro(3,6-dioxa-4-methyl-7-octenylsulfonyl fluoride) as disclosed in U.S. Patent No. 3,282,875. Also known as a copolymer of tfe and perfluoro(3-oxa-4-pentacene fluoride), as disclosed in U.S. Patent No. 4,358,545, the copolymer thus formed is hydrolyzed, usually through exposure. It is converted to an ionic polymer form in a suitable aqueous alkaline solution, as disclosed in U.S. Patent No. 3,282,875. Clocks, sodium and unloading are all suitable cations known in the related art to be suitable for the above listed ionic polymers. In the above enumerated polymers, the fluorine atom provides more than one benefit. The fluorine group on the carbon atom near the sulfonyl group in the side chain provides an electrical negativeity to give the cation sufficient instability to provide high ion 201241013 conductivity. (4) If the money is changed, the mobility of the miscellaneous seeds is greatly reduced, resulting in loss of conductivity. The polymeric flakes, which are typically associated with IUb polymers, also impart chemical and thermal stability to the fluorine atoms of rhodium. The above characteristics have proven to be extremely valuable in the application of the [Knocking Chlorine Test" process.

Watakabe et al., U.S. Patent No. 7, </RTI> <RTIgt;5</RTI> No. 8, discloses a body polymer electrolyte material which is a repeating unit comprising money as a substrate, which provides a Λ: let: have a -ester in the main chain The ring structure of the polymer "3 body B is a base-repeating unit-copolymer:; body B has the following formula: 或 early or X is - fluorine atom, a jj 2 where j is 0 atom a base The metal atom ^=)=, (wherein Mf is a hydrogen which may contain the ether oxygen atom straight 匕: and Rf is fluorinated. In spite of this disclosure, in the commercial 1, ^ C (four) poly properties are properly balanced The production process is not yet reached - the proper balance of the sub-conductivity. k, the initial and high off-times, in addition to the above requirements, there is also / the use of the electrode material is the ionic polymer is ~ dioxo In addition, it is preferred that the polymer is not easily soluble in water. It is preferable to use Λα' and Λ. It is not convenient to combine the characteristics of the heart-like features. The present invention provides an electrolyte material for application. Solid polymer electrolysis = 7 dimer poly 201241013 or multiple ionic polymers Comprising polymerized units A (below):?: (A) one or more fluorinated monomers, or

Eight 2 F2c

F

F

F and (b) polymerized units of one or more fluorinated monomers (B):

CF2=CF-0-[CF2]n-S02X wherein η is 2, 3, 4 or 5, X is F, Cl, rm X, 单价 单价 单价 ;; and wherein the ionic polymer is at 8 叱, The 95% penetration plane proton conductivity is greater than % ^S/Cm9' and its oxygen permeability at 23 ° C, relative humidity 〇% is greater than x 10 scc cm / (cm 2 s cmHg). In one embodiment, the ion &amp; material of the solid polymer electrolyte material further comprises one or more polymerized units of a fluorinated monomer (C) CF2=CF-〇-[CF2]m_CF3, wherein the claw is ruthenium Bu], 3 or 4. In one embodiment, the ionic polymer of the solid polymer electrolyte material further comprises polymerized units of fluorinated monomer (D) CF2 = CF2. 201241013 In one embodiment, the ionic polymer of the solid polymer electrolyte material contains less than 5 〇 carboxyl pendant groups or terminal groups per million carbon atoms of the polymer. In one embodiment, the ionic polymer of the solid polymer electrolyte material contains less than one pendant carboxyl group or terminal group per million carbon atoms of the polymer. In one embodiment, the ionic polymer of the solid electrolyte material contains less than 5 carboxy pendant or terminal groups per million carbon atoms of the polymer. In one embodiment, the 250-SOzX groups of the ionic polymer of the solid polymer (4) material are the terminal groups on the backbone of the polymer, per million carbon atoms of the polymer. In one embodiment, 50 to 1% of the polymer chain end groups of the ionic polymer of the solid polymer electrolyte material are _8〇2 fluorenyl, and X is F, Cl, OH or OM and wherein馗 is a monovalent cation. In the embodiment, the solid polymer electrolyte material of the polymer has 50 to 1% by weight of the polymer chain terminal group, which is followed by a 4 〇 2 keto-perfluoroalkyl group. Is F, C1, 〇H or 〇M and i is a monovalent cation. Ν In the embodiment, the ionic polymer of the solid polymer electrolyte material has X or F or C1' having a Tg measured using a thermal differential scanner (DSC) in the range of 100 to 250 °C. In one embodiment, the ionic polymer of the solid polymer electrolyte material has X being OH or OM' and having a Tg measured using a dynamic mechanical analysis (DMA) in the range of 200 to 270 °C. . 201241013 In one embodiment, when X is F4X in the C1 form, the ionic polymer of the solid polymer electrolyte material has a solubility in 23 cc of hexafluorobenzene of more than 15 grams per kilogram of hexafluorobenzene. In an embodiment, X is! When the ^ or \ is in the form of 0, the solubility of the ionic polymer of the solid polymer electrolyte material in hexafluorobenzene at 23 ° C is more than 100 g per kg of hexafluorobenzene. In one embodiment, the ionic polymer of the solid polymer electrolyte material has an equivalent weight ranging from 550 to 1400 grams. In one embodiment, the ionic polymer of the solid polymer electrolyte material has an equivalent weight ranging from 650 to 1100 grams. In some embodiments, more than one or more of the above characteristics may be present in an embodiment of the invention. For various embodiments of solid polymer electrolyte materials including a specified ionic polymer, there is also an embodiment wherein the solid polymer electrolyte material consists of or consists essentially of the specified ionic polymer. In one embodiment, the solid polymer electrolyte material of the present invention is applied as an electrochemical cell, such as one or more electrodes in a fuel cell. Further, in the case of a solid polymer electrolyte material described in each of the embodiments, the present invention also provides an electrode for a fuel cell comprising the solid polymer electrolyte material. The monomeric polymers used in the text are abbreviated as follows: PDD monomer is perfluorodimethyldioxole (monomer A; PFSVE monomer is CF2=CF0CF2CF2S02F; and PSEPVE monomer is CF2=CF0CF2CF ( CF3)0CF2CF2S02F. The TFE monomer is tetrafluoroethylene, CF2=CF2. 201241013 [Embodiment] Any list of preferred values at the lower end of the column, unless otherwise noted, includes the upper end preferred value and The endpoint, and the eve of the range, otherwise the range refers to the inclusion of the norm and it is not intended to be a defined integer and fraction. In addition to the present invention, all of the scopes set forth herein are intended to be specific to === Value. This small and maximum. Any combination, including the most so-called "fluorinated sulfonic acid polymer θ" with a highly fluorinated backbone and a two-band side chain attached to the backbone of the repetitive gamma "3; I.e. == to &gt; 90% of the polymer backbone and side chains are chaotic atoms. In another embodiment, the polymer is perfluorinated' means a peak atom attached to the backbone and side chains. And 100% of the total number of hydrogen atoms are fluorine atoms. The so-called "acid side group" means that it is flanked by a polymer backbone, a group that acts as a repeating side chain, and the side chain is terminated with a sulfonic acid functional-S〇3H. The polymer may have a small amount of acid functionality in the form of a salt or a 4-acid. Typically at least about 8 mole percent, more typically at least about 13 mole percent, or at least about 19 mole percent have pendant groups with sulfonic acid functionality. Here, 'polymer chain end group' refers to the polymer chain. End groups at each end of the length, but excluding pendant groups on the repetitive side chain. The term "ionic polymer" or "solid polymer electrolyte material" is used herein to include where X is F or X is C1. -S02x-based pre-201241013, the two-products can be acidified to a given acid form via hydrolysis (x = from % with the -S〇2X group in which X*OH or OM is present. Here, polymerization The composition of the composition is converted into a precursor polymer: the constituent monomer of the celestial element, and the _S〇2X base form is added by the accompanying text, for example, a polycondensation formed from PDD and PFSVE, including the -S〇2F group. , can be converted to -S03H based PFSVE ^. The sharpener precursor polymer is expressed as p(P DD/PFSVE), using text (or text) to indicate that the -so2x group is indeed in the form of fluorine (-so2f base) and the latter is called p(PDD/PFSVE), using text (or text description - The S〇2X group is in the acid form (-so3h group). That is to say, in the polymer, the unit refers to the original monomer (such as PFSVE) here, regardless of whether the polymer is in the form of a sulfonium fluoride or an acid. Herein, the "equivalent" of a polymer (ionic polymer) means that the weight of the polymer to be neutralized is neutralized, wherein the polymer is an acid form (pot acid) polymer, or the polymer is hydrolyzable and Acidification causes the -soA group to be converted to the acid form (_8〇3 printing). That is to say, in the polymer, the unit refers to the original monomer (e.g., PFSVE) herein, regardless of whether the polymer is in the form of a sulfonium fluoride or an acid. Here, the environmental conditions mean that the room temperature and pressure are 23 ° C and 760 mmHg. Unless otherwise stated, the glass transition temperature Tg of the ionic polymer is measured by dynamic mechanical analysis (DMA). The ionic polymer film is about 30 μηι to 100 μηη thick and is heated in a DMA instrument (ΤΑ Instruments, New Castle County, Delaware, USA, instrument model Q800) while oscillating at 1 Hz. . The temperature at the maximum wave ♦ in the function tan(5) is taken as the breaking temperature of 201241013 degrees. Again, the Tg described herein was measured using a thermal differential scanner (DSC). In this case, 'a small sample of ionic polymer (about 2 to 5 mg) is subjected to heat absorption analysis using DSC (TA Instruments, New Castle County, Delaware, USA), followed by heating and cooling. Release. The temperature at the midpoint of the secondary endothermic transition period on the secondary heating of the sample is taken as Tg. Here, the number average molecular weight Μη and the weight average molecular weight Mw are determined by the size exclusion chromatography (SEC) described below. The ionic polymers described herein are dispersed at elevated temperatures (as in Example 14), while the dispersion utilizes SEC (Waters Corporation, Milford, MA, USA, Integrated Multiple Detector Size Exclusion Chromatograph GPCV) /LS 2000TM) for analysis. Four SEC styrene-vinylbenzene columns (Shodex, Sakamoto Kawasaki) were used for separation: 1 protective column (kd -800P), 2 linear columns (KD -806M) and 1 used A column that increases the resolution of the polymer distribution high molecular weight region (KD-807). The chromatographic conditions were at a temperature of 70 °C. The flow rate was 1.00 ml/min, the injection volume was 2195 ml and the running time was 60 minutes. The column was calibrated using a pmmA narrow standard. The sample was diluted with a mobile phase of N,N-dimethylacetamide + 0.11% lithium chloride + 0.03% toluene to a weight percentage of 〇1 ,, and then injected into the column. Use a refractive index and viscosity detector. The refractive index reaction was analyzed using dn/dc of 0.0532 ml/g, which was judged by using other p(TFE/PFSVE) and P(TFE/PSEPVE) ionomers as appropriate characteristics samples of the government. Although the molecular weights recorded herein are not unity, molecular weights are reported in Dalton units in accordance with the relevant art. 201241013 In one embodiment, the solid polymer electrolyte material of the present invention is a copolymer (ionic polymer) comprising a polymer unit of a fluorinated vinyl group and a second fluorinated vinyl monomer B. Incorporation time, wherein the monomer A is a perfluorodioxole or perfluorodioxol monomer of the structure Αι or A2 (see below):

And the monomer B has a functional perfluoroolefin CF2=CF(0)[CF2]nS02X of a pendant fluoroalkylsulfonic acid group or a pendant fluoroalkylsulfonic acid group, wherein n ^2, 3, 4 or 5,乂 is a corpse, (: Bu (^ or 0 PCT and among them) ^ is a cadmium cation. The solid polymer electrolyte material is at 80 ΐ, and the relative wetness of 95% of the plane planar proton conductivity is greater than 7 〇 mS/em. And its oxygen permeability of $23 ° C 'relative humidity 0% is greater than 1 x 1 () - / cm / (cm 2 s cmHg). In one embodiment 'the solid polymer electrolyte material is in, for example, The permeation plane proton conductivity of 95% relative humidity is greater than 8〇mS/cm, while its oxygen permeability at 23°C and relative humidity 0% is greater than 2 X 10·9 see cm/(cm2 s cmHg) In one embodiment, the copolymer of the monomers A and B may further comprise the following formula (C) CF2=CF(0)[CF2]m(CF3) fluorinated monomer as the substrate _ weight 201241013 complex unit, wherein m is 〇, 1, 2, 3 or 4. Here, monomer C means PMVE (perfluoromethyl vinyl ether) for m = 0, and monomer refers to PEVE (perfluoro for m = 1) Ethyl vinyl ether). In another embodiment, the copolymer of monomers A and B may in turn comprise monomers D tetrafluoroethylene, CF2 = CF2, referred to herein as a heavy xjO of TFE, in an embodiment, the copolymer of monomers A and B may in turn comprise monomer C or monomer D, or A repeating unit of both. For the various embodiments in which the solid polymer electrolyte material is composed of a specific copolymer (ionic polymer), there is also a case where the solid polymer electrolyte material is substantially polymerized by the specified ion. An embodiment of the object, and an embodiment wherein the solid polymer electrolyte material comprises the specified ionic polymer. In one embodiment, the ionic polymer of the solid polymer electrolyte material comprises at least 30 moles Percentage, polymerized unit of one or more fluorinated monomers Ai or A2, or a combination thereof. In one embodiment, the ionic polymer of the solid polymer electrolyte material comprises at least 12 mole percent, one or more fluorinations Polymeric unit of monomer B. In one embodiment, the ionic polymer of the solid polymer electrolyte material comprises: (a) 51 to 85 mole percent, one or more fluorinated monomers Ai or A2, or a combination thereof of And (b) a polymerized unit of one or more fluorinated monomers B in a percentage of 15 to 49 moles. In such an embodiment, preferably monomer A is Al (PDD) and monomer B Then, it is PFSVE. 201241013 Knife ratio, or a plurality of fluorinated monomers B, a single U?9 mole, preferably monomer A is Al (pDD), and the monomer ^~ embodiment is implemented in another In the example, the solid polymer = FSVE. The t polymer comprises: ((10) to 85 moles per gram of the monomer Α Α 2 或其 2 or a combination thereof, or a plurality of fluorination ratios - or a plurality of fluorinated monomers 丄 : 丄 丄 49 49 耳 4 , , , , , , , , , , , , , , , 49 49 49 49 49 聚合 聚合 聚合 聚合 85 85 85 85 85 85 85 85 85 (b) i4 to / knife ratio '- or a plurality of polymerized units of fluorinated monomer B; = 49 mole percent, polymerization of one or more gasification monomers D. In yet another embodiment, the solid polymer electrolysis = ionic polymer comprises: (a) 2G to 85 mole percent, polymerized units of the monomer monomer Ad A2 or combinations thereof; (8) 14 to Mo = percentage, Polymeric units of one or more fluorinated monomers B; and k), polymerized units up to 49 mole percent, fluorinated monomer c or fluorinated monomer D, or combinations thereof. In one embodiment, the copolymer has a Μη greater than 60, 〇〇〇, preferably greater than 100,000. In one embodiment, the monomer oxime used in the polymerization reaction is CF2=CF(0)(CF2CF2)S02F (ie, 1! in the above formula is 2 and X is F), herein refers to PFSVE (full Fluroxysulfonyl vinyl ether). Indeed 14 201241013 Fluorine-based fluorine atoms can be replaced by other X groups using the methods discussed above. This portion can be achieved by first converting the -sot group in the monomer before the polymerization, but can also be easily achieved by converting the -S〇2F group in the polymer. The higher conductivity form of the copolymer has a sulfonic acid group, meaning that the sulfonium fluoride group (_so2f) is converted to a sulfonic acid group (-S03H). In one embodiment, the polymer can be fluorinated after polymerization to reduce the concentration of carbonyl fluoride, vinyl and/or carboxyl groups. The fluorination reaction can be carried out by exposing the polymer rubber powder of the formula -S〇2Fe to elemental fluorine as in the patent document GB1210794, or by drying first, then at 80 to 180. The temperature of (: is increased, and the fluorine-diluted fluorine gas is passed through the polymer. Here, the carboxyl group is defined as a carboxylic acid, a phthalic anhydride, a carboxylic acid dimer or a carboxylate. In an embodiment, The ionic polymer of the solid polymer electrolyte material comprises polymerized units of PDD and PFSVE monomers, wherein the PFSVE polymerized unit is in acid form (having a side sulfonic acid group, as described below). For the solid polymer electrolyte material of the present invention It is said that these ionic polymers have a higher oxygen permeability if they have a higher equivalent weight. Therefore, in an embodiment, the preferred equivalent range (g) may be as low as 600, or as low as 700, or low. Up to 800, or 900 grams, and up to 14 inches, or up to 1300, or 1200 grams. In this embodiment, the ionic polymer has an oxygen permeability of greater than 1 x at 23 ° C, relative humidity 〇%. 1〇_9scc Cm/(Cm2 s cmHg), preferably greater than 2 x 10-9 scc cm/(cm2 s cmHg), even greater than i〇x 10-9 scc cm/(cm2 s cmHg). Lower straightness facilitates higher electrical conductivity. Thus, in a preferred embodiment, the solid polymer is electrolyzed. The ionic polymer of the material comprises polymerized units of PDD and PFSVE monomers, wherein the 201241013 PFSVE polymerized unit is in acid form (having a side sulfonate group), and wherein the equivalent range (g) of the ionic polymer is as low as 600, or as low as 700, or 750 grams, and up to 1400, or as high as 1100, or 900 grams. In this embodiment, the ionic polymer penetrates planar proton conductivity at 80 ° C, 95% relative humidity It is greater than 70 mS/cm, preferably greater than 90 mS/cm, and even greater than 100 mS/cm. In one embodiment, the ionic polymer has an oxygen permeability of greater than 10 X at 23 ° C and a relative humidity of 0%. 10·9 see cm/cm2 s cmHg. In one embodiment, the ionic polymer of the solid polymer electrolyte material has a penetration plane proton conductivity of greater than 70 mS/cm at 80 ° C and a relative humidity of 95%. And at 23 ° C, the oxygen permeability of 0% relative humidity is greater than 2 X 1 CT9 see cm / (cm 2 s cmHg), and even greater than 1 〇 X ι 〇 9 see cm / (cm 2 s cmHg). The ionic polymer of the solid polymer electrolyte material has a penetrating planar proton conductivity of 80% at 80 ° C and a relative humidity of 95%. For greater than 90 mS/cm and at 23 Ϊ, the relative humidity 〇% of oxygen permeability ^ is greater than 2 X ΙΟ·9 scc cm / (cm 2 s cmHg), and even greater than 1 〇χ 9 see cm / (cm 2 s cmHg) ° : In the examples, the ionic polymer of the solid polymer electrolyte material has a penetrating planar proton conductivity of 80% at 80 ° C and a relative humidity of 95 mS/cm. - a fluoropolymer comprising a S02X group (wherein 乂 is _ 素); first converted to a sulphate form by hydrolysis known in the art of phase correlation; (S 〇 3) ° (4) can be used in the nucleus polymer Enter the light in the form of a judgement or _. For example: when the fluorocarbon group is immersed in m: temperature, 25 «Benol hydroxy scent in about $201241013, then rinse the mash twice in 9 〇t deionized water, each rinsing about 30 to about 6G minutes It can be hydrolyzed and converted into two sodium forms. Another possible method is to use 6 to 2 〇〇 / ❶ aqueous metal hydroxide solution and 5 to 40% polar organic solvent such as DMSO, contact for 5 minutes at 5 〇 to 1 ,, then rinse for 1 〇 . After hydrolysis, the polymer "compound film" can then be converted to an acid form by finally contacting the polymer: a salt solution of the desired cation, and finally converting to an acid form (·8〇3Η) The steps can be carried out by contacting with a nitric acid-like acid and then rinsing. = The solid polymer electrolyte material of the place may be suitable as a sub-family membrane, such as a proton exchange membrane fuel, or a correction. (4) Polymer electrolytes such as: found to be used as fuel cell electrodes 'especially on the cathode, for example as ionic conductors and binders in the catalyst layer. = (the ionic polymer) can use any conventional method Shape, but not limited to view and solution or dispersion thin film technology. The film is changed as required for the intended application. The film typically has a small thickness. If the church I, more typically about 10 microns to about 175 microns, does not need nt 'The film may be two or more polymers, such as two (or one or more film) laminates. Such a film may be formed from 2 in solution stacks or in multiple laminate component compositions. When the film is a layer , the additional poly-characteristics, and the properties of the composition, and any of the chemical properties of the laminate, which may be identical or different. For the purpose, the term "membrane" is a term commonly used in the relevant field. , 201241013 or "Board" is synonymous and refers to the same item as the more general term "film" in the broader field. The film may optionally include a porous support for improving mechanical properties, reducing cost and other reasons. The porous support can be made from a wide range of materials such as plain weave, basket weaving, leno weaving or other various weaving, but the woven fabric or weaving of the secret material can be made from glass, such as a woman. A hydrocarbon polymer of a hydrocarbon such as polyethylene or polypropylene or a perhalogenated polymer such as polygastrifluoroethylene. A porous inorganic or terrarium material may also be used. To resist thermal and chemical degradation, the support Preferably, it is made of a fluorinated polymer, more preferably made of a perfluoropolymer. For example, the perfluoropolymer of the porous support may be a polytetrafluoroethylene (PTFE), or a tetrafluoroethylene and a CF2. =CFCnF2n+i (n = i to 5) Or a microporous film of a copolymer of (CF2=CFO-(CF2CF(CF3)0)mCnF2n+1 (m = 〇15, „=ι to Μ). Microporous pTFE films and sheets are known to be suitable as support layers A unidirectionally stretched film comprising at least 40% voids is disclosed in U.S. Patent No. 3,664, 915. A porous PTFE film containing at least 70% voids is disclosed in U.S. Patent Nos. 3,953,566, 3,962,153 and 4,187,390. The polymer dispersion can be combined by coating the support onto the support such that the coating is on the outer surface of the support while also dispersing into the inner pores. Alternatively, additional soaking can result in a thin film system. The laminate is to one side or both sides of the porous support. When the polymer dispersion is applied to a relatively non-polar support, such as a microporous PTFE film, an interfacial surfactant can be used to aid in wetting and intimate contact between the dispersion and the support. The support may be treated with a surfactant prior to contact with the dispersion or may be added to the dispersion. A preferred surfactant is the cation 201241013 ionized murine surfactant&apos; such as Zonyl 8 or CapstoneTM from DuPont, Wilmington, Delaware, USA. A preferred fluorinated surfactant is Zonyl® FS 1033D (CapstoneTM FS-10) sodium sulphate. In one embodiment, the film system can be subjected to an "adjustment" that can include the film undergoing heat or pressure prior to use, and can be as described in US Patent Application No. 2009/0068528 A1, in a liquid or gas such as water or Vapor ^ is carried out underneath. A potential consequence of this approach is that the mash is prepared in a favorable, fully hydrated form. "Full hydration" means that the cockroach contains substantially the maximum water content it can contain under normal pressure. The membrane system can be hydrated by any known method, but is usually immersed in an aqueous solution above room temperature and up to 1 〇〇 C. Usually, the aqueous solution is an acidic solution such as a 10 to 15% aqueous solution of nitric acid, which can then optionally be washed with pure water to remove excess acid. The soaking operation should be carried out at a temperature above 60 ° C, more typically above 8 〇 f for at least 15 minutes, more typically at least 30 minutes, allowing the hydration to be fully hydrated under atmospheric pressure. The solid polymer electrolyte material described herein can be used in combination with a fuel cell using a proton exchange membrane (also referred to as "PEM"). Example 3 hydrogen fuel cell, reformed hydrogen fuel cell, direct methanol fuel electric / or other organic / air fuel cell (such as ethanol, propanol, di- or diethyl hydrazine, formic acid, such as acetic acid and other tannic acid systems, etc. Organic; =::=Component_). The == described herein is found in batteries used to electrolyze water to form hydrogen and oxygen. The fuel cell is often formed into a stacked stack of ΜΕΑ, selected: d sub ί, a cathode and a cathode electrode, and the other, the μ fuel cell usually also includes a porous conductive sheet, the 201241013 porous turn The electric sheet is electrically connected to each electrode to the electrode m M / Di Ying expansion body is called a body expansion layer, a gas base substrate or a gas application catalyst is also called an electrocatalyst coating or (cl Π上' _ is referred to as a catalyst-coated film, and the lining battery can _(4) diffuse support ^), ,, ° &amp; CCM to form a loose MEA. The mic battery can also include a membrane that can be combined with a gas diffusion electrode (GDE) in the catalyst to form a consolidated MEA. The fuel cell consists of a single MEA or multiple MEA series stacked MEA, which is formed by a porous and conductive anode and cathode gas stray domain material, doped with the MEA edge and also forms an electrically insulating layer of pad #, such as A current collecting plate of a lithographic ink plate with a gas flow field, an end plate with a tie rod for fuel cell bonding, an anode inlet and outlet for a fuel such as hydrogen, a cathode gas inlet, and, for example, air The oxidant is made of an outlet. The crucible and the fuel cell thus formed are known in the related art. A suitable embodiment is described herein. The ionic polymer film is used to form a crucible by combining the crucible with a catalyst layer comprising a catalyst which is unsupported or supported on particles such as platinum particles, such as platinum or platinum cobalt alloy, and the present invention The same proton conductive adhesive as the ionic polymer' and a gas diffusion support. The catalyst layer can be made from known conductivity, catalytically active particles or materials, and can be made by methods known in the relevant art. The catalyst layer can be formed into a film which is a polymer of a binder for a catalyst particle. The binder polymer can be a hydrophobic polymer, a hydrophilic polymer or a mixture of such polymers. The binder polymer is typically an ionic polymer and may be the same ionic polymer as the membrane 20 201241013, or an ionomer that is different from the membrane. In one or more of the above embodiments, the solid polymer electrolyte material of the present invention is a binder polymer in the catalyst layer. Therefore, the ionic polymer of the present invention can be found to be applied to an upper electrode in a fuel cell. The catalytic layer can be applied from a catalyst paste or ink to a suitable substrate for use in the MEA. The method of applying the catalyst layer is not) The focus of the practice of the present invention is that a catalyst coating technique can be used to produce a substantially wide range of thicknesses from substantially as thick as 3 〇μπι to less than 1 μπι below. Various application layers. Typical manufacturing techniques include applying a catalyst ink or paste to a polymer exchange membrane or gas diffusion substrate. Additionally, an electrode decal can be prepared and then transferred to the film or gas diffusion support layer. Suitable methods for applying the catalyst to the substrate include spraying, painting, spacer coating, and screen printing or offset printing. Preferably, the anode and cathode electrodes have a thickness in the range of from about 1 to about 3 micrometers, more preferably less than about 25 micrometers. The thickness of the applied layer is dependent on the compositional factors and the process used to create the layer. The composition factors include the metal content on the coated substrate, the void ratio (porosity) of the layer, the amount of polymer/ion polymer used, the polymer/ionic polymer density, and the carbon support. The process used to create the layer (e.g., hot stamping corresponding to printing on dry or dry conditions) may affect porosity and thus the layer thickness. In one embodiment, a catalyst coating film is formed such that the thin electrode layer is directly attached to the opposite side of the proton parent exchange film. In a method of preparation, the electrode layer is sprayed onto a planar release substrate, such as a Kapton 8 polyimine film (available from DuPont, Inc., Irvine, Delaware 21 201241013). Prepared as a decal. The actuating force and optional thermal energy are transferred to the contact surface, and then removed, the substrate is released to form a CCM with a catalyst controlling the thickness and catalyst distribution. The film may be θ, ς when the electrode decal is transferred to the film, or the system may be dried or partially dried before being transferred. Further, the catalyst ink can be directly applied to the film by a printing method, after which the catalyst film is dried at a temperature exceeding 200 Torr. The resulting CCM system is then combined with a gas diffusion support substrate to form a loose crucible. &quot;&quot;&apos; In the formation of a catalyst print comprising an ionic polymer of the invention, the ionic polymer may be in the form -S02X. After forming the catalyst layer, ruthenium or catalyzed-GDB, the ionic polymer in the electrode can be hydrolyzed to convert to the salt form - SCMDM1 (usually Μι is Na+, κ+ or other monovalent cations, but Μ1 is not Η+ Then, the optional cation exchange is used to replace the cation Μ1 with a suitable cation Μ2. For example, Μ2 is Η+ for ρεμ fuel cells, Μ2 is Ν&amp;+ for gas base and the like. Further, the ionic polymer system can be first converted into an ionic form, S〇2〇M, and then dissolved or dispersed in a suitable solvent, which is then formed by the addition of an electrocatalyst and other additives, and then allowed to be electrode, MEA or catalyzed. _GDB is formed, followed by replacement of the cation M1 with an optional cation (M2) as appropriate. An example of a second method is the exchange of an ionic polymer dispersion into -S〇2〇lV with a ruthenium tetraalkylammonium ion, which may increase the melt flow of the ionomer, thereby facilitating The formation of the film, the catalyst layer is pasted &amp; hot pressed onto the film' followed by acidification to obtain -S〇2〇H ^ type 22 201241013 = A poly H3H form also (four) used in the transfer of electricity Material ί=Τ does not exceed 2°°. ‘= f 160C will be implemented in conjunction with ΜΕΑ. The gas 2 pack 'multi-secret conductive material, made of surface cloth or tilted and made: De: can be selectively treated to exhibit hydrophilic or hydrophobic behavior, coated with ▼ gas diffusion layer - side or two: body = , granules and PTFE-containing gas polymers 4, :::. The gas diffusion support material suitable for use in the present invention, and i is a commercial or commercial method. Suitable gas diffusion support material Easy B-TEK company). (The ionic polymer of the present invention in Natick, MA, USA exhibits a higher ionic conductivity. Because of any of the polymers of the present invention, it can be found that (iv) is an electrochemical solid polymer electrolyte material, or as a fuel cell, for example. The electrode is composed of a plurality of electrodes. Therefore, the present invention also provides a fuel cell or a plurality of electrodes comprising the solid D material of the embodiment described herein. The ionic polymer of the present invention also exhibits Very high oxygen permeability makes it particularly suitable as a cathode composition. The following abbreviations have been used for the examples: 5 23 201241013 E2 : FreonTM E2 Solvent, CF3CF2CF2OCF(CF3)CF2OCFHCF3 EW : Equivalent Fll : CFC13 FC-40 : FluorinertTM Electronic Fluid (3M Company): Mixture, mainly N(CF2CF2CF2CF3)3 and N(CF3)(CF2CF2CF2CF3)2 OTB: hexafluorobenzene HFPO dimer peroxide: cf3cf2cf2ocf(cf3)(c=o)oo(c=o Cf(cf3)ocf2cf2c f3 IBP: isobutyl sulfoxide, (ch3) 2ch (c=o)oo(c=o)ch(ch3)2 Μη : number average molecular weight

Mw : weight average molecular weight PDD : perfluorodimercaptodioxole

PFSVE : CF2=CF0CF2CF2S02F PMVE : Perfluoromethyl vinyl ether, CF2=CF(0)CF3 psepve : cf2=cfocf2cf(cf3)ocf2cf2so2f

RSU : FS02CF2C0F RSUP : fso2cf2(c=o)oo(c=o)cf2so2f SFP : fo2scf2cf2ocf(cf3)cf2ocf(cf3)(c=o)oo(c=o)cf( cf3)ocf2cf(cf3)ocf2cf2so2f

Teflon®: DuPont trademark TFE: tetrafluoroethylene, CF2=CF2

VertrelTM XF: CF3CFHCFHCF2CF3 (Miller-Stephenson Chemical Company, Danbury, CT) 24 201241013 Water: Deionized Water (Mibo-QPlus System, Billerica, MA) J MiUi Shell Example 1. Synthesis of p(PDD/PFSVE) in a ratio of 72.1: 27 9 Add a magnetic stir bar to a vial and then to a few vials of serum. The sample vial was accessed through a needle, shampooed with nitrogen, and the vial was frozen and dried, then 8 ml of pDD was injected; and 17.5 liter of pfsVE was added. The cold water in the vial was sprayed with n2 for 1 'main. Finally, 1 ml was injected and dissolved in VertreFM XF for about M 2 M = bell' dimer peroxide. The N2 positive pressure is applied to the Fp(R) bottle through the serocontainer, so that the sample bottle can magnetically stir the contents to/orphan. After 3 hours, the reaction mixture in the vial had been smashed and it was difficult to stir with magnetic force. After 2 to 3 days, refill the ΗmlΗ/ρ(^ polymer peroxide solution, then shake the vial by hand. The reaction mixture did not show any additional increase overnight (four). The contents were transferred to a dish lined with a Tefl〇n8 film (E I. du Pont de Nemours and Company, Wilmington, Ddaware). The reaction mixture was blown for several hours. The volatiles were removed and the dish was placed in a 100 to 120 C vacuum oven overnight. This produced 15 grams of a hard white foamed polymer (in the form of fluorine, _S02F). The polymer was analyzed as follows: Intrinsic viscosity : hexafluoro stupid is 0.384 dl / g

Tg 135C, measured by DSC '2 times heating, 1 〇. 〇/minute, N2 25 II 201241013

Composition (by NMR): 72.1 mole percent pdd, 27.9 mole percent PFSVE Hydrolyzed to -S〇3H form molecular weight: Mn = 167,057 Mw = 240,706 Examples 2 to 8. PDD/PFSVE polymer synthesis according to the example 1 Other polymers (sulfonium fluoride form, -SOJ) series prepared by the same method are shown in the following table. The above example 1 is also included in the table. The order within the table is arranged in descending order of PDD content. Table 1.

Tg_not shown in Table 1 was determined using Dsc for the precursor polymer (i.e., the polymer was in the form -s〇2X and X was F). Comparative Example 1, p (pDD/pSEpVE) with a ratio of 69 4: 3 〇 6 + Add the magnetic stir bar to a 1 oz glass bottle and cover the glass bottle with a serum stopper. Lang_access is through the injection needle, minus (4) 26 201241013 rinse, dry ice to freeze the glass bottle, then inject 9.3 grams of PDD, then inject 31.4 grams of PSEPVE. (PSEPVE is abbreviated to PSVE in the related art of CF2=cfocf2cf(cf3)ocf2cf2so2f or perfluorosulfonylethoxypropyl vinyl ether'). The frozen liquid A in the glass bottle was sprayed for 1 minute, and finally 1 ml was injected, and about 0.2 Μ of HFPO dimer peroxide dissolved in vertrelTM XF. The needle through the seropreg is adjusted to provide a positive pressure of Ν2 to the vial so that the vial can be warmed to room temperature by magnetically stirring the contents. By the next day, the reaction mixture in the glass bottle had thickened to be difficult to stir with magnetic force. After standing at room temperature for 2 to 3 days, the contents of the vial were stirred into 1 mL of CF^CI^CFzCH3 to produce a fluid upper layer which would pour out the gel-like lower layer. The gelatinous lower layer was transferred to a dish lined with a Tefl〇n® film. The gel was blown with nitrogen for several hours to remove volatile components, and the dish was placed in an 80 C vacuum supply tank for 2 to 3 days. Thus, 12.5 g of a hard white foamy polymer (sulfonyl fluoride form, -S02F) was produced. This polymer was analyzed as follows:

Composition (using fluorine NMR): PFD of 69.4 mole percent; 30.6 Percentage of PSEPVE intrinsic viscosity: 0.149 dl/g in HFB Dissolve 3 g of polymer in 27 g of HFB to form a solution, then use 0.45 μm The membrane filter was filtered and then cast into a Kapton® polyfilm (DuPont) using a 760 micron (30 mil) razor. The film will crack when dry. Adding a lower boiling point fluorinated solvent to the HFB solution to form an additional/liquid mixture as a latent film plasticizer, for example, using a 1:10 ratio of E2·polymer, or a ratio of 1:1〇 Perfluorophenanthrene (Flutec PPllTM from F2 Chemical Co., Ltd., Pres 27, UK 201241013): Polymer. After washing and allowing HFB to evaporate, 'these films will also crack. ^The polymer of Comparative Example 1 cannot be washed with HFB solution to form a film without the need for a support. Otherwise, each of Examples 1 to 8 will be after casting the HFB solution. A film is formed which does not require a support. Comparative Example 2. Non-copolymerization of PDD/PSEPVE using an IBP initiator a. Preparation of an initiator, isobutyl sulfoxide (IBP). A solution of 78 liters of CFsCHzCFfH3 and 7.93 g of granules dissolved in 56 mL of deionized water was placed in a three-necked flask. After the anti-acquisition is cold, the mixture is added to 12.3 ml, 30% peroxidic gas should be two: with a mild exotherm. Once the reaction mixture had returned, 7.8 ml of vaporized isobutyl hydrazine was dissolved in 13 ml of the resulting solution while maintaining the reaction mixture below 1 〇〇c. After the ruthenium mixture was stirred for another 10 minutes, the separated lower layer was allowed to pass through a 0,4 5 micron filter, and the device was subjected to heterogeneous. The oxidized isobutylene containing 0-10 mol was obtained by the titration method.醯 (IBp) b, use IBP initiator 'to make PDD unable to copolymerize with psEpvE. Add - magnetic stir bar to - small noodle bottle, then cover the glass bottle with serum plug. The access of the glass bottle is through batch Shoot the needle, (N2) rinse, freeze the glass bottle with dry ice, then inject 9 〇 2 g pDD, T^PSEPVE 〇 ^^^^ spray! minutes, finally inject 2.0 ml, dissolved in CF3CH2CF2CH3 about 0.1 Μ IBP. The N2 positive pressure is supplied through the sero-injection vial' to allow the glass bottle to be warmed by magnetic money: 28 201241013 to room temperature. Since no significant viscosity is produced after 3 days, in the 3rd, 4th, 5th An additional 2 ml of IB·1 Μ IBP sample was injected into a total of 8 ml, 0.1 M IBP. After 6 days, the reaction mixture was added to 1 〇〇ml of CFgCHzCFzCH3 to produce the remaining precipitate, which was dried and then reduced. 0.03 g of residue. Use of hydrocarbon as initiator to initiate formation of PDD/PSEPV The polymerization of the E copolymer is problematic. In addition, the hydrocarbon initiator causes the hydrocarbon segment to be inserted into the terminal group of the polymer chain (for example, IBp causes the (CH3) 2CH-terminal group on the gasified polymer). It is expected that there will be chemical degradation under fuel cell conditions, shortening the polymer life. Therefore, a perfluoroinitiator compound is preferred (such as the FPO dimer peroxide used in Example 1). Example 9. With -CF (CF3) Preparation of p(pdd/pfsve) a. Initiator SFP at the end of CF2CF2S02F. 7.92 g of potassium hydroxide particles dissolved in 56 ml of water were placed in a 500 ml flask cooled to 〇 ° C. The flask was refilled with 156 ml of VertrdTM and 12.3 ml of 30% aqueous hydrogen peroxide under continuous ice bath. 22 ml of fso2cf2cf2ocf2cf(cf3)ocf(cf3)(c=o)f, as soon as possible, The solution formed in 26 ml of VertrelTM XF was added while maintaining the temperature of the water bath at 10 to 15 ° C. After 0 to 1 (the TC was stirred for another 1 minute, the separated organic layer was quickly passed through the crucible). _45 micron passer. The filter droplet is set to contain 0.185 IV [ Peroxidized SFP (see the abbreviation above).

S 29 201241013 b. Using the initiator SFP, p(PDD/PFSVE) is allowed to initiate the reaction. Add a magnetic stir bar to a 2 ounce glass bottle, then cover the glass bottle with a serum plug. The access to the glass bottle is through the injection needle, flushing with nitrogen (N2), freezing the glass bottle with dry ice, and then 8 ml PDD. Next, 17.5 g of the frozen liquid in the PFSVE(glass bottle) was injected for 2 minutes, and finally 1 ml of SFP dissolved in VertrelTM XF of about 0.185 Torr was injected, and then the mixture was sprayed with Ν2 for 1 minute. The needle that passes through the sero-plug is adjusted to provide a positive pressure of Ν2 to the glass bottle to warm the glass to room temperature. After 64 hours at room temperature, the reaction mixture had thickened to be difficult to stir with magnetic force. Transfer the contents of the vial to a Teflon®-coated dish, blow it off with A for one day to remove volatiles, and place it overnight in an i〇〇〇c vacuum oven. Thus 13.5 g of a white polymer (sulfonyl fluoride form '-S02F) was produced. Composition (by NMR): 67.2 mole percent PDD; 33.8 mole percent PFSVE with SFP polymer chain end groups. Example 10. p(pdd/PFSVE) with -CF2S02F end a. Preparation of initiator RSUP. The flask equipped with a magnetic stir bar was cooled to near 〇 ° C ' and then loaded with 2.8 g of sodium carbonate and 90 ml of VertrelTM XF ' of 35 mM (6.3 g) of FS02CF2 (C = 0) F ("RSU"). After stirring at 〇 ° C under a positive pressure of nitrogen for 3 hours, the reaction mixture was passed through 20 g of anhydrous calcium sulfate (W. A. Hammond, Drierite, Drierite, USA) and then passed through a 0.45 micron filter. The droplet is fixed to be RSUP with 0.124 、, [FS02CF2(C=〇)〇〇(C=0)CF2S02F]. 30 201241013 b. Use the initiator RSUP to cause p(PDD/PFSVE) to initiate a reaction. Add a magnetic stir bar to a 2 ounce glass bottle and cover the glass via a serum stopper. The glass bottle was accessed by injecting a needle, rinsing with nitrogen, freezing the glass via dry ice, then 8 ml of PDD, followed by injecting 17.5 g of PFSVE. The frozen liquid in the glass bottle was sprayed with n2 for 1 minute, and finally 1.5 ml of RSUP dissolved in VertrelTM XF of about 0.124 Torr was injected, and the mixture was sprayed for 1 minute. Adjust the needle through the sero-plug to provide a positive pressure of Ν2 to the glass bottle to warm the glass to room temperature. After 64 hours at room temperature, the reaction mixture was allowed to remove volatiles leaving a hard residue (nitrogen positive pressure removed most of the volatile solvent). Transfer the contents of the vial to a Teflon®-plated dish, blow it with N2 for one day, and place it overnight in a 10 〇t vacuum oven. This produced 5.5 g of a white polymer (sulfonyl fluoride form, _s〇2F). Composition (by NMR): 66% mole percent pdd; 34.0 mole percent PFSVE with RSUP polymer chain end groups. PDD utilizes a free radical mechanism and PFSVE for copolymerization. Initially, free radical R* is added to the PDD or PFSVE monomer, resulting in a new free radical RM* that adds additional monomer. The new monomer continues to increase until the two free radical couplings cause the polymerization to terminate, producing the final independent polymer 'R(M)n+1-(M)m+1R. Peroxide + R* radical R* + M + RM* RM* + nM ^ R(M)n+1* (peroxide decomposition) (initiation by polymerization) (polymer chain growth, reproduction) 201241013 R( M) n+1* + *(M)m+1R + R(M)n+1, (M)m+1R (terminating) The r group at both ends of the chain is derived from the initiator. Peroxides such as SFp and RSUP will leave a _8 〇 group at the end of the polymer chain (for example, see Example 44B of U.S. Patent No. 5,831,131), and vice versa such as HFPO dimer peroxide and iBp bow | The hair spray does not produce a -SOe end group, as summarized in Table 2 below. Initiator end group end group type IBP (CH3)2CH-hydrocarbylalkyl HFPO cf3cf2cf2ocf(cf3)-perfluoroalkyl RSUP fso2cf2- perfluoroalkyl SFP with -S02F fso2cf2cf2ocf2cf(cf3)ocf(cf3)-^band Before the -502? perfluoroalkyl group is used as the proton exchange membrane or electrode of the fuel cell, the sulfonium fluorofunctionality is first converted to the acid group. Higher acid-base concentrations result in higher proton conductivity (see Table 4; lower equivalents, resulting in higher proton conductivity). In one embodiment, from 50 to 100% of the polymer chain end groups of the ionic polymer are -S〇2F groups. In one embodiment, 50 to 1% of the polymer chain end groups of the ionic polymer are -s〇2x groups, wherein X is F, C OH or OM and wherein hydrazine is a monovalent cation. In one embodiment, 50 to 100% of the polymer chain end groups of the ionic polymer are perfluoroalkyl hydrazino terminated with -SO# groups. In one embodiment, the polymer chain end groups of the ionic polymer The middle 50 to 1% is a perfluoroalkyl group in which 32 201241013 -S〇2X is used, wherein X is p, ci, 〇H or 〇M and wherein Μ is a monovalent cation. Example 11. Synthesis of terpolymer PDD/PFSVE/TFE terpolymer: 24 g of pDD and gram of PFSVE' were placed in a 400 ml reaction vessel and then cooled to -30 °C. Next - step, add 2 grams of TFE liquid to the far valley. Finally, 15.5 grams of a 10% HFPO dimer peroxide initiator solution dissolved in yertrei 8 χ ρ solvent was added, and the container was then sealed and placed in an oscillator. The reactor was heated to 30 ° C and maintained for 4 hours. The reactor was emptied and rinsed, and the reaction mixture was recovered. The container is rinsed and the rinse is added to the reaction mixture. The mixture was placed on a rotary evaporator to isolate the solid; 23 g of a white solid polymer (sulfonyl fluoride form, -S〇2F) was obtained. NMR analysis indicated that the polymer composition was 46.1 mole percent PDD, 32.5 mole percent pFSVE, and 21.3 mole percent TFE. 40% of the solids in the material were dissolved in HFB, followed by dilution with FC-40 to increase viscosity and form a casting solution. A film of nearly 125 microns (nearly 5 mils) was cast, and the film was sturdy and elasticity. The preparation of other PDD/PFSVE/TFE polymers is similar to that shown in Table 3.

S 33 201241013 Table 3. Synthesis of PDD/PFSVE/TFE terpolymers Polymer PDD (g) Reaction TFE (g) Feed PFSVE (g) HFPO (g/solution) 1 Polymer yield (g) ί PDD Molar percentage n composition knot j TFE mole percentage PFSVE Molar percentage equivalent (g) 11A 9.0 2.0 65.2 3.5 17 29.3% 40.9% 29.7% 656 11B 15.5 4.0 107.0 5.9 12 43.7% 17.2% 39.1% 595 11C 24.7 2.0 107.0 15.5 23 46.1% 21.3% 32.5% 689 11D 46.1 2.0 130.7 20.7 61 54.3% 17.8% 28.0% 815 11E 82.2 6.0 278.0 32.0 62 57.5% 10.4% ----- 32.1% 747 11F 92.7 3.0 278.0 32.0 63 59.9% 7.17% 32.9% 744 HFPO dimer peroxide initiator solution, 0.2 Μ PDD/PFSVE/PMVE terpolymer: 27.8 g in a 400 ml reaction vessel! &gt;1)1:) and 924

Gram PFSVE' then cooled to -30 °C. The next step was to add 6.4 grams of PMVE liquid to the container. Finally, 8-8 grams of a 10% HFPO dimer peroxide initiator solution dissolved in E2 solvent was added, and the contents were sealed and placed in the earthquake. The reactor was heated to 3 ° C and maintained for 4 hours. The reactor was emptied and rinsed, then the anti-broad mixture was recovered, rinsed, and the rinse was added to the reaction mixture. The mixture was placed on a rotary evaporator to isolate the solid; 16 g of a brittle white solid was obtained. NMR analysis indicated that the polymer composition was 63.4 mole percent PDD, 32.0 mole percent PFSVE, and 4.6 mole percent PMVE (sulfonyl fluoride form, -SOJ). 40% of the solids in the material were dissolved in HFB, followed by dilution with FC-40 to increase the viscosity and form a casting solution. A film of approximately 2012-041313 125 microns (nearly 5 mils) was cast and the film was strong and resilient. The preparation of other PDD/PFSVE/PMVE polymers is similar to that shown in Table 4.聋4. PDD/PFSVE/PMVE ternary $polymer 厶忐 polymer PDD molar percentage PMVE molar percentage PFSVE molar percentage equivalent (g) 11G 63.4% 4.6% 32.0% 785 11H 57.2% 6.5% 36.3% 692 111 58.4% 15.8% 25.8% 932 11J 49.6% 24.5% 25.9% 902 11K 52.4% 13.6% 34.0% 720 11L 44.8% 21.2% 34.0% 703 11M 55.1% 14.3% 30.6% 795 1 IN 47.3% 22.3% 30.4% 779 110 53.4% 15.3% 31.3% 775 IIP 48.8% 23.6% 27.6% 851 Example 12. Analysis of Fluorine NMR Composition of Polymer

The copolymer of Example 5 was analyzed by i9F-NMR (19f_nmr) at 470 mega. At 3 ° C, a 60 mg sample dissolved in hexafluorobenzene (HFB) was used to obtain a map. The coaxial tube with c/cfc13 is inserted into the NMR official's as a reference for locking and chemical displacement, respectively. The peak at 43 Ppm is caused by PSFVE's -S02F and its intensity is 10035 (absorption unit). Several peaks were observed between nearly 72 and nearly 88 ppm, caused by both -CF3 (of pDD(6F)) and _〇(:172 (of PFSVE(2F)), with a total intensity of 2177〇7qPFSVE ST· 35 The molar fraction of 201241013 was judged as 100035/[ [(217707-2(100035))/6] + 100035} = 23.4%. When hydrolyzed, the equivalent (EW) was estimated to be (0.766*243.98 + 0.234*277.95) /0.234 = 1077. A similar analysis was performed for other copolymers, which is presented in Table 1 to determine its composition. Example 13. Conversion of sulfonium fluoro group to sulfonic acid group and measurement of conductivity The copolymer in Example 6 was Prepared in a similar manner as in Example 1 except that the scale was doubled, using 16 ml PDD, 35 ml PFSVE and 2 ml initiator solution (see Table 1 &gt; 19F-NMR analysis indicated 30.5 mole percent PFSVE and EW 834. The fluorine form (-SOJ) copolymer (36 grams) was dissolved in HFB to form a 15 weight percent solution, which was then transitioned using a 1 micron filter. A razor blade with a south gate of 760 microns (30 mils) was then used. Cast this solution to Kapton® Polyimide Film (DuPont, Wilmington, DE) Then, HFB will volatilize at room temperature to produce a transparent film. After separation from Kapton®, let the film and film fragments (31.7 grams total) at ll ° ° C 'potassium hydroxide: dimethyl sulfoxide: Water (with a percentage of heavy weight of 10:20:70) was heated for 24 hours to hydrolyze into a quinone form. A film with a thickness of 112 microns was examined using Fourier-transmission infrared spectroscopy and the results showed no at 1472 cm-1. The peak corresponding to the sulfonium fluoride appeared, indicating that the hydrolysis was completed. The film piece was rinsed in water, filtered, and then a smaller fragment was recovered and dried under vacuum overnight to obtain 3 L of 33 g of the hydrolyzed thin mold. In acid form (-S〇3H), immerse it in 8 (TC, 20% by weight nitric acid for 1 hour. After initial immersion, replace with fresh nitric acid, then make a second 1 hour soak. Place the film on Rinse in water of the beaker for 15 minutes y 36 During the period of 201241013, the water is continuously replaced, and the pH of the water in the straight cup is kept neutral. The larger pieces and film fragments recovered by filtration are placed in a 1 °C vacuum oven. Drying, heavy The new weighed, which yielded 28.2 grams of polymer in acid form. The reduced weight was judged by the loss of lost film fragments and filter paper, meaning that the polymer itself was least dissolved. Using the current through the plane perpendicular to the film plane Technique, measuring the temperature rise of the ionic polymer acid form of Example 6 to control the RH conductivity. The lower electrode was formed with a non-shaft rod of 12.7 mm, and the upper electrode was formed with a stainless steel rod of 6.35 mm diameter. The rod was cut to the desired length, polished and gold plated. The lower electrode has 6 slots (〇 68 mm wide and 0.68 mm deep) to allow moisture to flow. A stack consists of a lower electrode / GDE / membrane / GDE / upper electrode. GDE (Gas Diffusion Electrode) is a catalyzed ELAT® (De Sumster, New Jersey, USA)

Nora North America's E-TEK division, which includes a carbon cloth with a microporous layer, a platinum catalyst, and a 〇 6 to 0_8 mg/cm 2 Nafion® applied to the catalyst layer. A lower diameter of 95 mm is punched through the lower GDE, and a magnetic diameter of 6,35 mm is punched through the film and the upper GDE to match the upper electrode. The stack was assembled and maintained in place within a 46.0 mm X 21.0 mm X 15.5 mm block of annealed glass reinforced fiber processable polyetheretherketone (PEEK) having a 12.7 mm diameter hole drilled into the bottom of the block. To accept the lower electrode and a concentric 6.4 mm diameter hole drilled to the top of the block to receive the upper electrode. The ρ ΕΕΚ block also has a straight threaded terminal. The female thread paired with the Ο-ring seal tube (1M1SC2 and 2 M1SC2 of Parker Instruments) is used to connect to variable moisture. The fixture is placed in a small tiger head with a plastic handle, and then a torsion wrench is used to apply a torque of 10 pounds. Connect the holder of 37 201241013 with the membrane to the 1/16&quot;tube (moisture injection) and 1/8 of the inside of the forced convection oven for heating, and the tube (moisture discharge) Measured with a thermocouple. Use a pump controller to allow water to be injected from the ISC0 model 5〇〇D injection pump. Allow dry air to be calibrated from the mass flow controller (p-sink [lamp F201' is equipped with Tylan®R〇- 28 control box) injection (maximum 2〇〇seem). To ensure evaporation of water, the air and water mixture is circulated in a 1.6 mm (1/16&quot;) and i.25 m long stainless steel tube box in the oven. The resulting humidified air is injected to the 1/16&quot;tube inlet. The battery pressure (atmosphere) is measured using a Druck8PDCR4010 pressure sensor equipped with a DPI 280 digital pressure display. Under ideal gas behavior, liquid water is used. The vapor pressure is calculated as a function of temperature, the gas composition from the two flow rates, the vessel temperature, and the battery pressure, etc. The relative humidity is calculated. The grooves in the lower electrode allow humidified air to flow to the membrane, achieving rapid equilibrium with water vapor. .package The AC impedance Rs of the actual part of the fixture of the film is based on the Solartron SI 1260 impedance/gain phase analyzer equipped with ZView 2 and zPlot 2 software and the SI 1287 electrochemical impedance (UK F14 0NR Hampshire, Farnborough) Solartron Analytical Inc., measured at 1 kHz. The AC resistance Rf of the short part of the fixture is also measured by the actual part of the AC impedance measurement at 1 kHz for fixing the unassembled film sample. The conductivity and κ of the film are then calculated as: k = &quot;((Rs _ Rf) * 0.317 cm2), where "the film thickness is in centimeters. 38 201241013 In the water _'cooled to room temperature, the money will be three wet lakes' special film stacked in the solid, the total height is micron. The ionic polymer of Example 6 is moist (four) 离子 ion conductivity at room temperature after measurement It is 153 mS/cm. It is heated to 8 〇 and the relative humidity is controlled at 25, 50 and 95%. The plane conductivity of the plane is measured to be 5 5, 27 and 99 mS/cm. Planar conductivity is also measured in a similar manner. Example 14. Ionization Preparation of the dispersion of the acid form (2 gram) of the acid form (2 gram of the polymer), 36.0 grams of ethanol, 143.1 grams of water, and a sample of the acid form of Example 13 were placed in a 400 ml Hastelloy shaker tube. 〇9 gram of 3 〇% by weight of Zonyl® FS 1033D, CF3(CF2)5(CH2)2SO3H dissolved in water. Close the shaker tube and heat it up to 270 °C at 124 minutes after execution Temperature and pressure of li82psi. The heater was turned off and then cooled; the shaking salt; the tube reached 269.7 C at 134 minutes after execution and cooled to 146 °C 149 minutes after execution. After returning to ambient conditions, the liquid dispersion was poured into a can, and the shaker tube was rinsed with a solvent mixture of 20:80 water using an additional 8 grams of fresh ethanol, and then the rinse was mixed with the dispersion. The dispersion was filtered through a polypropylene filter cloth having a gas permeability of 25 cfm (Sigma Aldrich, St. Louis, MO), and the weight of the dispersion after filtration was determined to be 261 g. The solvent was removed from the 1.231 grams of ionic polymer dispersion sample by drying in a vacuum oven to yield 0.0895 grams of solid. The solids content was calculated to be 7 3 〇/〇, meaning that 19 grams of the original 20 grams of polymer was dissolved and recovered. 39 201241013 The method of removing unwanted cations (mainly metal ions) from the ionic polymer dispersion is as follows: ion exchange resin beads (DowexTM M-31, 600 from Dow Chemical Company, Midland, MI, USA) The cleaning method is carried out by extraction method, first refluxing with 300 g of ethanol for 2.4 hours, followed by 400 g, n-propanol to water with a ratio of 75:25 for 4.5 hours, and then replacing 400 g of fresh propanol to water ratio. The same was refluxed for another 6 hours. At the end of the third extraction, the color of the solvent was significantly lighter than that of the second time. The cooled resin beads are rinsed with water and then stored in a plastic bottle. A small glass chromatography column was charged with 5 ml of cleaned, wetted resin beads. The column was rinsed with 1 mL of 15% hydrochloric acid to ensure that the acid salt was in acid form, then water was allowed to flow through the column until the pH reached 5 or more, followed by 1 mL of n-propanol. The ionic polymer dispersion was passed through the column and 100 ml of n-propanol was passed through. The eluent was checked with a pH test paper to determine when the acid form of the ionic polymer no longer flowed out of the column. The purified dispersion solid was determined to be 6.7%. The aliquot of the dispersion was aliquoted at 1 liter per 1 liter (:, initial 200 mbar pressure and then slowly lowered to a rotary evaporator at 7 mbar pressure for concentration. Solids now 8 4% (n-propanol content is 50% after measurement by infrared spectrometer). U.S. Patent No. 6,150,426 shows a perfluoroionic polymer which is dispersed at a high temperature and which is similar to the application in this example, which can be polymerized. Composition of each particle of the molecule. The dispersion was analyzed by a size exclusion chromatography performed at 7 G ° C. The movement was carried out using hydrazine, hydrazine dimethyl acetamide + hydrazine 11% lithium chloride + 0.03% toluene sulfonic acid. The sample is diluted to a weight of 〇1〇 and then injected into the column. The refractive index and viscosity detector are used. The refractive index reaction is dn/dc analysis using 0_0532 ml/g, which is 201241013 using other p(TFE/ A suitable characteristic sample of the PFSVE) and p(TFE/PSEPVE) ionic polymer dispersions was determined. The p(PDD/PFSVE) polymer herein has a number average molecular weight Μη of 132,000 and a weight average molecular weight Mw of 168,000. Each polymer uses the same procedure 0 Example 15. Oxygen permeability and conductivity 19 F-NMR analysis of the copolymer in the form of -SOzF in Example 4, indicating a mole percentage of 23 PFSVE, or an EW of 1095. The copolymer of Example 4 was cast from a HFB solution into a film which was then hydrolyzed. Acid exchange was performed using a similar method as used in Example 13. The oxygen permeability of the replicate film was designed using an instrument designed to measure high oxygen permeability films (Moeon Ox-Tran®, Minneapolis, Minnesota, USA) 'Measured at 23 ° C and relative humidity 〇 %. The oxygen permeability of a 58 μm thick film is 14.5 X 10 9 see cm/cm 2 s cmHg, while the oxygen permeability of a 62 μm thick film is 15. 〇X 1 s cmHg. The acid form copolymer film of Example 4 was evaluated using a mechanical mechanical separation method at a temperature between -50 and 252 (at a frequency of 1 Hz. The storage modulus was 1388 MPa at 25 t: Dropped to &amp; MPa at 15 ° C. The small peak at tanS (near 〇〇 3 on the baseline) was observed at u ° C. αηδ increased rapidly above 220, reaching 252 at '252tK· 7 'the same _ storage modulus is 29 gigapascal. The analysis is not - temperature implementation, so the county View _ _ with material temperature _: and drop. The sample becomes weak (perfluorosulfonic acid group is known to be at 25 (the above rc will decompose). The glass transition temperature of this sample, which is usually specified as full = 201241013 The ionic polymer Corresponding to the largest peak in tan5, the sample is above 250 °C, but is estimated to be lower than 260 °C (by comparing the other tan5 peak shapes of the formula p(TFE/PFSVE) ionic polymer) &lt; The proton conductivity of the acid form ionic polymer is measured according to the above formula (Example 13). Table 5 shows the oxygen and conductivity results for some ionic polymers. Table 5. Oxygen permeability and conductivity of some acid forms of PDD/PFSVE ionic polymer Ionic polymer labeled polymer composition (PDD / PFSVE) Solid % Total EW Μ ( (k) Mw (k) Tg1 DMA 透Oxygen 23 °C 0% RH E-9 see cm/cm2 s cmHg Guide. 25 % RH Pen 8 ( nS/cm 50 % RH ) °C 95 % RH Example 2 81.0/19.0 1320 44 Example 3 79.1/20.9 1201 18 1.1 9.1 Example 4 77.0/23.0 6.4% 1095 143 212 to 257 15 52 2 Example 5 76.6/23.4 1077 14.7 Example 1 72.1/27.9 9.8% 908 201 289 ~237 6.0 5.3 25 Example 63 69.5/30.5 10.8% 834 132 168 -213 5.5 27 Example 73 63.9/36.1 712 Example 8 56.5/43.5 595 _ The Tg system shown in Table 5 was measured by DMA to determine the acid form of the ionic polymer (ie _s〇3h form polymer). Example 4 Conductivity is measured at room temperature with a water wet film. Examples 6 and 7 were prepared on a larger scale than other polymers, with all reactants/reagents scaled up to 2 fold. 42 201241013 Preparation of PDD/PSEPVE-like polymers is problematic. The polymerization of a monomer using a hydrocarbon initiator (IBP) has a very low yield. The resulting polymer was hydrolyzed, acidified, and then a dispersion was prepared according to Examples and 14. The molecular weight Mn measured by SEC chromatography was 112,000, and the Tg was 178 ° C (measured by DSC). The equivalent weight measured by 19F-NMR at 470 MHz was 970 g, which corresponds to a monomer ratio of 68 3 PDD / 31.7 PSEPVE. However, the film from the dispersion is brittle, has some cracks, and cannot obtain a film which does not require a support. Repeated polymerization using a perfluoro initiator (HFPO dimer peroxide) was also problematic (Comparative Example 1). The polymer obtained was dissolved in HFB in an attempt to form a film directly from the solvent solution. However, the film broke again upon drying (even with the addition of a plasticizer), and a film without a support was not obtained. The fully immersed acid form of the polymer (this sample was prepared by hot pressing at 225 C) had a plane electrical conductivity of 84 mS/cm at room temperature and was measured by 19F-NMR at 470 MHz. The equivalent weight is 997 grams, which is equivalent to the monomer ratio of 69.4 PDD/30.6 PSEPVE. The p(PDD/PFSVE) ionic polymer (acid form) has much higher oxygen permeability than p(TFE/PSEPVE) (traditional Nafion®) or p(TFE/PFSVE) ionic polymer (acid form), such as discuss. Comparative Examples 3 to 11 p (TFE/PFSVE) and p (TFE/PSEPVE) Ionomers Comparative Example 3: Tetrafluoroethylene (TFE) and PFSVE systems in a blocked 1 liter Hastelloy reactor at 35 ° C The copolymerization reaction was carried out with 2,3-dihydroperfluoropentane (Vertrel® XF). At the beginning of the polymerization, all PFSVEs will be added to 43 201241013. Continuously pumping the cooled initiator [2 W3_tetragas-2·(heptafluoropropanyl)-1-ketopropyl]peroxide (hfp〇 dimer peroxide) into the reactor, TFE was added to maintain the pressure at 105 psi. The polymerization time was nearly 8 minutes. The polymer was hydrolyzed and acidified as follows: A sulfonium fluoroform (about 157 g) was charged into a 2-liter three-necked round bottom flask equipped with a glass mechanical stir bar, reflux condenser and stopper. An equal weight (about 157 g) of ethanol and 85% of a potassium hydroxide solution (about 157 g) were added to the flask depending on the weight of the load, and an additional 3.67 times by weight of water (about 577 g) was added. Thus a suspension containing 15 weight percent polymer, 15 weight percent potassium hydroxide (85 weight percent solution), 15 weight percent ethanol and 55 weight percent water was produced, and the suspension was heated to reflux. About 7 hours. The polymer was collected after vacuum filtration using a polypropylene filter cloth. The polymer was rinsed in a flask by heating it to 80 ° C with 4 volumes of water (about 600 ml), and then the residue on the filter cloth was collected. After rinsing 4 times with water, a polymer in the form of potassium sulfonate is produced. The potassium sulfonate polymer was then rinsed for a period of one hour by heating it to 80 ° C with 4 volumes of 20% nitric acid (about 6 liters of water: 123 ml of 70% nitric acid, diluted to 600 ml). The polymer on the filter cloth was collected and heated to 80 with 4 volumes of water (about 600 ml). (: to rinse the polymer, then collect the residue on the filter cloth. Repeat the nitric acid/water rinse procedure 4 times to convert the acid in the form of the acid to the sulfonic acid form polymer. Then 4 times the volume The amount of water (about 600 ml) is heated to 80 ° C to rinse the polymer, and then the residue on the filter cloth is collected until the rinse is neutral (pH > 5). Let the polymer use air on the filter cloth. Dry, then sputum p into a glass jar in a vacuum oven at 60 ° C under nitrogen gas 201241013, then dry it in the middle. Transfer the polymer to the crucible, then dry (16 g), avoid absorption Moisture.... The dispersion of the copolymer in air is made in the following manner (1000 rpm) in an i-liter Hastelloy pressure vessel; when 1TTM is heated for more than 3 hours, reaching 25 〇ΐ, The pressure at this point was 738 psi, and then the vessel was evacuated from the chamber 2, then the vessel was rinsed with 15 grams of n-propanol, and the rinse and dispersion were mixed after the absence. Some small amounts of polymer were still not Disperse,, - some are on both sides of the wetting and transfer Dissipated; 87% of the loaded polymer was recovered from the dispersion. An additional 355 grams of n-propanol and 155 grams of water were added to the dispersion. The lysate was purified on an ion exchange column, similar to Example 14 The method used a 7 Torr rotary evaporator to remove the ethanol and concentrate the dispersion until the ionic polymer concentration was 5.6 weight percent. The dispersion was cast onto the Kapton 8 film using a doctor blade having a 127 mm gate height. Then, it was dried at room temperature under nitrogen purge. The second casting was carried out on the top of the first casting, and then washed with N2 and dried at room temperature. After heating in a 17 °c oven for 5 minutes, the film was dried. The acid form ionic polymer film is removed from the Kapton® polyimide film (DuPont) to produce a 45 μm τ thick ionic polymer film. The glass transition temperature is measured using DMA' and the equivalent is It is determined by titrating a total acidity determined by a film sample, and oxygen permeability is measured according to the method of Example 15 (see Table 6 below).

S 45 201241013 Comparative Examples 3 to 5 are all TFE/PFSVE ionic polymers. The ionic polymers of Comparative Examples 4 and 5 were prepared in a similar manner to Comparative Example 3, but the TFE pressure was adjusted at the time of polymerization to obtain different equivalents. Comparative Examples 6 to 11 ionic polymers were all TFE/PSEPVE ionic polymers. Table 6. Oxygen permeability comparison of TFE/PFSVE and TFE/PSEPVE ionic polymers. Percentage of polymer moles TFE/PFSVE or TFE / PSEPVE EW (g) τε °c 〇2 permeability 23〇C; 〇% RH E -9 see cm/cm2 s cmHg 3 p(TFE/PFSVE) 82.0/18.0 734 117 0.081 4 p(TFE/PFSVE) 80.0/20.0 677 118 0.076 5 p(TFE/PFSVE) 81.5/18.5 720 117 0.053 6 p( TFE/PSEPVE) 87.5/12.5 980 102 0.136 7 p(TFE/PSEPVE) 86.6/13.4 924 100 0.102 8 p(TFE/PSEPVE) 87.4/12.6 .972 103 0.098 9 p(TFE/PSEPVE) 87.3/12.7 963 97 0.120 10 p(TFE/PSEPVE) 86.8/13.2 934 101 0.119 11 p(TFE/PSEPVE) 84.8/15.2 837 100 0.057 All the polymers shown here (Table 6) are in acid form (ie polymer in the form -S03H) The Tg (Table 6) shown here is obtained by measuring the acid form ionic polymer by DMA. The ionic polymers used in Comparative Examples 6 and 7 are commercially available Nafion® acid form dispersions DE2020 and DE2029, both available from DuPont (Wilmington, DE). The initial polymer of Comparative Example 8 was a commercially available yttrium fluoride form Nafion® resin. It was hydrolyzed, acidified and dispersed, and then subjected to a similar procedure of Comparative Example 3 to carry out a sub-exchange of 46 201241013 'the difference was at 23 (TC was dispersed, and the dispersion was concentrated to 23 weight percent. S02F of Comparative Examples 9 to 11) Form P (TFE/PFSVE) polymer was polymerized using a similar monomer and polyandation reaction method as described in U.S. Patent No. 3,282,875. The preparation of the acid form dispersion was similar to Comparative Example 8. Comparative Examples 6 to 11 The steps of forming a film from the dispersion were similar to those of Comparative Example 3, except that a sufficient film was formed only from a single casting (because the dispersion concentration was high, about 20 to 23% solids), and the film The combined temperature was 150 ° C. Figure 1 shows a plot of the oxygen permeability data for Tables 5 and 6 plotted against the ionic polymer equivalents. Data show that PDD/PFSVE ionic polymers (Examples 1 through 5) Oxygen permeability is much higher than that of TFE/PFSVE or TFE/PSEPVE ionic polymer (Comparative Examples 3 to 5 and Comparative Examples 6 to 11, respectively). Trying to make PDD/PSEPVE ionic polymer film (Comparative Examples 1 to 2) Not successful because the film will rupture In order to obtain high oxygen permeability, the PDD/PFSVE ionic polymer preferably comprises between 60 and 85% PDD monomer units, more preferably between 70 and 85%, still more preferably between 75 and 85%. However, in order to achieve a favorable balance between high conductivity and high oxygen permeability, Table 5 shows that the PDD/PFSVE ionic polymer preferably contains between 6 〇 and 80% of the PDD monomer unit, and is better Between 60 and 75% or between 60 and 70%. Table 1 shows that this copolymer has a PDD content between 56.5 and 81%. The lower limit of PDD content was found to be about 56% PDD. Table 5 shows the PDD range. The lower limit of the PDD/PFSVE ionic polymer, which has an equivalent weight of 595 ' or 56.5% PDD. However, after hydrolysis, acidification, s 47 201241013 and then rinsing with water, it was found that most of the polymer was lost during the water rinse' and The copolymer is widely soluble in water. The above ionic polymer was found to be useful as a solid polymer electrolyte material for use as an ionic conductor and binder in fuel cell cathodes. Example 16. Stability in Corresponding to Ion Polymer Degradation Related Fields Some perfluorosulfonic acid ion polymerization has been reported Degradation occurs during battery operation, and it is believed that this chemical degradation reaction is carried out by hydroxyl or peroxy radical species. Fent〇n measurement has been shown to simulate this type of chemical degradation reaction (see, for example, 2 〇〇 5 years of publication "Fuel Cell", Vol. 5, No. 2, pp. 302-308, J. Healy et al., "Chemical Degradation of pFSA Ionomers in PEM Fuel Cells"). The solid polymer electrolyte material of the present invention described herein was evaluated for its chemical degradation phenomenon using a Fenton test to compare the difference between the PDD/PFSVE ionic polymer of the present invention and the PDD/PSEPVE ionic polymer. ~ Synthesis of PDD/PSEPVE: Three PDD/PSEPVE ionic polymers were prepared using the HFPO dimer peroxide initiator and the following procedure. A magnetic stir bar was added to a reaction flask and the flask was capped with serum. The flask was accessed by squeezing the needle, rinsing with nitrogen (N2), freezing the flask with dry ice, then injecting the PDD, followed by injection of PSEPVE, as indicated in Table 7 below. The frozen liquid in the flask was sprayed with N2, and finally HFPO dimer peroxide dissolved in about 0.25 Torr in vertrelTM XF solvent was injected. Nitrogen gas was maintained in the flask&apos; so the flask was allowed to warm by stirring the contents of the flask 48 201241013 to room temperature. After 1 day, another aliquot was injected and then mixed in a (four) mixing manner. After 丨PC&gt;-polymer peroxidation rotary evaporation ϋ, while separating the polymer, the flask was transferred to one to 12 (TC vacuum oven overnight, so that the polymer was placed in the 8 〇 polymer system according to the following steps) The composition of the material is determined by fluorine NMR, and is determined by the form of a polymeric gel permeation chromatograph. The specific molecular weight is determined by using the lattice. "Parts and results are listed in the synthesis below.

The hydrolyzed (protonated form) polymer taken from the operation of the first, about 53.53 g was tested for its peroxide degradation rate by the Fenton method. The polymer was allowed to dry, weighed again and placed in a test tube. A mixture of 425 g of hydrogen peroxide (Η2〇2) and 6.2 mg of ferrous sulfate (FeS〇4) was added to the test tube. A stir bar was placed in the test tube to maintain the polymer in a submerged state. The tube was then heated to 80 ° C and maintained at this temperature for 18 hours. After 18 hours, the tube was allowed to cool and the solution was separated from the polymer. The concentration of the image ions in the solution was then tested using a fluorine electrode and a millivolt meter. The polymer was allowed to dry and weighed&apos; and then placed back into the fresh H2〇2/FeS〇4 mixture&apos; for an additional 18 hours at 8 °C. The second analysis was repeated on the second s 49 201241013, and then the process and the analysis were repeated for the third time. Using the material balance concept, the fluoride ion concentration can be converted to a total fluorine release rate. The total fluorine emissions of this PDD/PSEPVE sample was 20.8 mg F7 g polymer. As a control, two similar PDD/PFSVE polymers were produced using the above process, with a larger reaction vessel and three initiator additions. The total initiator used was 1.48 ml of initiator / (X monomer moles), compared to 1.45 ml of initiator / (x monomer moles) used in Execution 1 above, where X is 2 different The total number of identical monomer moles used in ionic polymers, PDD/PSEPVE and PDD/PFSVE. The synthesis details of the PDD/PFSVE ionic polymer are shown in Table 8 below. Table 8_ Synthesis of PDD/PFSVE Ionic Polymers Executions # ml PDD cc PFSVE ml Initiator (Day 1) ML Initiator (Day 2) ML Initiator (Day 3) G Polymer Molar Percent PDD Molecular Weight (M„) Molecular Weight (Mw) 4 100 225 8.0 6.0 4.0 222 67.3% 110,468 150.093 The molecular weight of the PDD/PFSVE ionic polymer is 50% less than that of the PDD/PSEPVE ionic polymer of the first to third embodiments. The difference in molecular weight indicates that the terminal group of the PDD/PFSVE ionic polymer (execution item 4) is clearly less than the PDD/PSEPVE ionic polymer (executives 1 to 3.) In fact, the maximum number of terminal groups can be estimated from The PDD/PFSVE ionic polymer (execution 4) is 495, and the PDD/PSEPVE ionic polymer (executive 1, 2, and 3) 50 201241013 are 808, 838, and similar. 76 g of this PDD/PFSVE polymerization is tested as above (10) reagent. The total fluorine emission of this sample is 5/78 mg F·/g. The PDD/PFSVE ionic polymer is so low in fluorine. In terms of release amount, it is confirmed that the number of terminal groups is small, making PDD/PFSVE away. The polymer has excellent stability, that is, its chemical degradation is lower than that of PDD/PSEPVE ionic polymer. [Simplified schematic] Figure 1 depicts a series of P(PDD/PFSVE), p(TFE/PFSVE) and p (TFE/PSEPVE) When the ionic polymer is in an acid form, the oxygen permeability (Y-axis) of the ionic polymer film corresponds to the ionic polymer equivalent (X-axis). [Key element symbol description] None

Claims (1)

201241013 VII. Patent Application Range: 1. A solid polymer electrolyte material for use in an electrode of a fuel cell, comprising one or more ionic polymers comprising: (a) - or a plurality of fluorinated monomers VIII or Aggregate unit of VIII; Αι A2 And (b) - or a polymerized unit of a plurality of fluorinated monomers (B): (B) CF2 = CF-0 - [CF2] n - S02X wherein 11 is 2, 3, 4 or 5, 乂 is a corpse, 0 , 011 or 〇]^, and wherein Μ is a monovalent cation; and wherein the ionic polymer has a penetration plane proton conductivity of greater than 70 mS/cm at 80 ° C and a relative humidity of 95%, and is at 23° C, a relative oxygen permeability of 0% of an oxygen permeability is greater than 1 X HT9 see cm / (cm2 s cmHg) ° 2. The solid polymer electrolyte material of claim 1, wherein the ionic polymer further comprises one or Polymerized unit of a plurality of fluorinated monomers (C): 52 201241013 (C) CF2=CF-〇.[CF2]m.CF3 wherein m is 〇, i, 2, 3 or 4, a solid polymer electrolyte material, Wherein the ion cluster comprises a polymeric unit of the fluorinated precursor (D): CF2=CF2. 4:::: Item "Solid polymer electrolyte material", wherein the polymer = 10,000 carbon atoms, the ionic polymer contains less than 5 羧基 carboxyl side groups or terminal groups. The solid polymer electrolyte material, wherein among the one million carbon atoms of the polymer, the ionic polymer contains more than 25 β β 2X groups, and it serves as a terminal group on the polymer backbone, wherein X疋Cl, 〇Η or ΟΜ and wherein VI is a monovalent cation. 6. The solid polymer electrolyte material according to claim ,, wherein the ionic polymer has 50 to 1 末端 in the terminal group of the polymer chain /0 is a _8〇2\ group, wherein X 疋 F, α, ΟΗ or ΟΜ and wherein μ is a monovalent cation. 7. The solid polymer electrolyte material according to claim 1, wherein the ionic polymer 50 to 100% of the terminal group of the polymer chain is a perfluoroalkyl group which is terminated by a _S〇2x group, wherein X is F, Q, OH or OM and wherein μ is a monovalent cation. 53 201241013 8. As requested 丨The solid polymer electrolyte material, wherein the ionic polymer has X or F or gas And having a Tg of between 10 Torr and 25 CTC, which is measured by a thermal differential scanner (DSC). The solid polymer electrolyte material of claim 1, wherein the ionic polymer has X Is OH or 〇M, and has a Tg of between 2 〇〇 and 270 ° C as measured by dynamic mechanical analysis (dmA). 1〇_Solid polymer as claimed in claim 1 The electrolyte material, wherein X is F or X is in the form of C1, the solubility of the ionic polymer in 23 ° C, hexafluorobenzene is more than 15 grams per kilogram of hexafluorobenzene. 11 -bu . The solid polymer electrolyte material, wherein χ is F or X is in the form of Cl, the solubility of the ionic polymer in 23 ΐ, hexafluorobenzene is more than 100 grams per kilogram of hexafluorobenzene. 12 &gt;&gt; The solid polymer electrolyte material according to the item 1, wherein the ionic polymer has an equivalent weight in the range of 550 to 1400 g. The solid polymer electrolyte material according to Item 1, wherein the ion The equivalent of one hydrate is in the range of 650 to 1100 g. 14. = solid polymerization as described in item 1. An electrolyte material, wherein the ion compound comprises one or more fluorinated monomers of at least 3 G. or a polymerized unit of VIII or a combination thereof. 54 201241013 15. The solid polymer electrolyte material of claim 1. Wherein the ionic polymer comprises at least 12 mole percent of one or more polymerized units of fluorinated monomer B. 16. The solid polymer electrolyte material of claim 1 wherein the ionic polymer comprises: a polymerized unit of between 51 and 85 mole percent or a plurality of fluorinated monomers VIII or A2 or a combination thereof; and (b) one or more fluorinated monomers ranging from 15 to 49 mole percent The polymerization unit of B. 17. The solid polymer electrolyte material of claim 2, wherein the ionic polymer comprises: (a) a polymerized unit of one of 20 to 85 mole percent or a plurality of fluorinated monomers A2 or a combination thereof; (b) a polymerized unit of one or more fluorinated monomers B of between 14 and 49 mole percent; and (c) a polymerized unit of one or more of fluorinated monomers C of from 0.1 to 49 mole percent . 18. The solid polymer electrolyte material of claim 3, wherein the ionic polymer comprises: (a) a polymerized unit of one of 20 to 85 mole percent or a plurality of fluorinated monomers Aii A2 or a combination thereof (b) a polymerized unit of between 14 and 49 mole percent or more of fluorinated monomer B; and 55 201241013 (c) one of 0.1 to 49 mole percent or more fluorinated monomer D Aggregate unit. The use of the solid polymer electrolyte material according to any one of claims 1 to 18, which is applied to an electrode in a fuel cell. An electrode in a fuel cell, comprising the solid polymer electrolyte material according to any one of claims 1 to 18. 56