TW200903890A - Solid polymer electrolyte - Google Patents

Abstract

Disclosed are: a solid polymer electrolyte comprising 100 parts by mass of a rigid heterocyclic polymer and 0.1 to 100 parts by mass of at least one acid selected from the group consisting of phosphoric acid, polyphosphoric acid, sulfuric acid and methanesulfonic acid, wherein the rigid heterocyclic polymer mainly comprises at least one repeating unit selected from the group consisting of the repeating units represented by the formulae (I) and (II) and a repeating unit represented by the formula (III), and wherein the mole-based copolymerization ratio among the repeating units (I), (II) and (III) (i.e., a (III)/((I)+(II)) ratio) ranges from 0 to 5 (inclusive) and the inherent viscosity is 0.05 to 100 dl/g as measured in a sulfuric acid solution at a concentration of 0.5 g/100 ml at 25 DEG C; ; a solid polymer electrolyte composition comprising the solid polymer electrolyte and a polymer having an ionic conductivity; a solid polymer electrolyte membrane comprising the solid polymer electrolyte or the solid polymer electrolyte composition; a membrane/electrode assembly using the solid polymer electrolyte membrane; and a fuel cell using the membrane/electrolyte assembly.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid polymer electrolyte which is excellent in ion conductivity and oxidation resistance, and is composed of the solid polymer electrolyte and a polymer having ion conductivity. A solid polymer electrolyte membrane formed of any of the solid polymer electrolyte composition, a membrane/electrode assembly using the solid polymer electrolyte membrane, and a fuel cell using the membrane/electrode assembly. [Prior Art] A solid polymer electrolyte is a solid polymer material having an electrolyte group in a polymer chain, and is strongly bonded to a specific ion, and is formed into a particle 'fiber by selectively permeating a cation or an anion property. It is used in various applications such as electrodialysis, diffusion dialysis, and battery separator. The fuel cell is provided with a pair of electrodes on both sides of the ion conductive solid polymer electrolyte membrane, and is supplied to the electrode (fuel electrode) on one side by using hydrogen gas or methanol as a fuel, and is supplied as an oxidant by oxygen gas or air to the other electrode. An electrode (air electrode) on one side obtains an electromotive force. Further, in water electrolysis, hydrogen and oxygen are produced by electrolyzing water using a solid polymer electrolyte membrane. Perfluorosulfonic acid membrane with high ion conductivity known from the trade names of Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark of Asahi Kasei Co., Ltd.), Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.) The fluorine-based electrolyte membrane is widely used as a solid polymer electrolyte membrane such as a fuel cell or water electrolysis because it has excellent stability in chemical -5 to 200903890. Further, 'salt electrolysis is to produce sodium hydroxide, chlorine and hydrogen by electrolyzing an aqueous sodium chloride solution using a solid polymer electrolyte membrane. In this case, since the solid polymer electrolyte membrane is exposed to chlorine and a high-temperature, high-concentration aqueous sodium hydroxide solution, it is not possible to use a hydrocarbon-based electrolyte membrane having insufficient resistance. Therefore, in the solid polymer electrolyte membrane for salt electrolysis, it is generally resistant to chlorine and a high-temperature, high-concentration sodium hydroxide aqueous solution, and further, a part of the carboxylic acid group is introduced into the surface to prevent reverse diffusion of the generated ions. Fluorosulfonic acid membrane 0 However, the fluorine-based electrolyte which represents a perfluorosulfonic acid membrane has a chemical stability which is very large by having a C - F bond, and is used in addition to the above-mentioned solid fuel cell, water electrolysis, or salt electrolysis. In addition to the polymer electrolyte membrane, it is also used as a solid polymer electrolyte membrane for hydrohalic acid electrolysis, and is further applied to a humidity sensor, a gas sensor, an oxygen concentrator, etc. by ion conductivity. However, fluorine-based electrolytes have the disadvantage of being difficult to manufacture and very expensive. Therefore, in the past, the fluorine-based electrolyte membrane was used in a limited-use application such as a solid polymer fuel cell for the use of a space or a military, and it is used as a low-nuclear power source for a vehicle. Use is difficult. Therefore, as an inexpensive solid polymer electrolyte membrane, an electrolyte membrane in which an aromatic hydrocarbon polymer representing an engineering plastic is sulfonated is proposed. (For example, refer to Patent Documents 1, 2, 3, 4, and 5). When the aromatic hydrocarbon-based electrolyte membrane obtained by sulfonating these engineering plastics is compared with the fluorine-based electrolyte membrane of Nafion -6 - 200903890, the former has an advantage of being easy to manufacture and low in cost. However, there are also very weak disadvantages in terms of oxidation resistance. According to Non-Patent Document 1, it has been reported that, for example, a sulfonated polyetheretherketone or a polyether oxime is degraded from an ether moiety adjacent to a sulfonic acid. Therefore, it is considered that when an electron-donating group is present in the vicinity of the sulfonic acid, oxidation degradation is started from there. Therefore, in order to improve the oxidation resistance, a sulfonated polyphenylene hydrazide in which the main chain consists only of an electron attracting group and an aromatic ring is proposed (Patent Document 6), and a sulfonic acid is introduced into the adjacent portion of the sulfonic acid group. Sulfonated polyfluorene (Non-Patent Document 2). However, according to Patent Document 7, deterioration of the aromatic hydrocarbon-based electrolyte membrane is oxidative degradation, and sulfonic acid which is directly bonded to the aromatic ring as an ion-conductive substituent is considered to be based on a strong acid and is detached at a high temperature to conduct ion conduction. The case where the rate is lowered is also one of the reasons. For example, the sulfonated polyphenylhydrazine or the sulfonated polyfluorene in Patent Document 6 or Non-Patent Document 2 cannot avoid deterioration due to detachment of the sulfonic acid. Therefore, the ionic conductive substituent is not expected to be a sulfonic acid, and in Patent Document 7, it is proposed to use an alkylsulfonic acid instead of a sulfonic acid. This is effective for improving the ionic conductivity reduction due to the detachment of the sulfonic acid, but the main chain of the aromatic polymer used has poor oxidation resistance due to the electron-donating group. On the other hand, the azole-based polymer is expected to be a polymer having excellent heat resistance and chemical resistance as a solid electrolyte membrane for a fuel cell. As the azole-based polymer having ion conductivity, for example, a sulfonated azole-based polymer has been reported (Patent Document 8). However, as described above, the sulfonic acid group introduced into the aromatic ring by using the polymer as a raw material is liable to cause a desulfonic acid reaction due to acid or heat. The use of the electrolyte membrane as a fuel cell is not sufficient. Further, in Patent Documents 9 to 11, there has been reported an electrolyte membrane for a fuel cell in which polybenzimidazole-based polymer polybenzimidazole is obtained by using a polyphosphoric acid coating material (dope). Japanese Patent Publication No. Hei 9-245818 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei No. Hei 9-245818 (Patent Document 3) Japanese Patent Publication No. Hei 1 1 - 1 6 6 6 7 (Patent Document 4) Japanese Patent Laid-Open Publication No. JP-A-2002-110174 (Patent Document No. JP-A-2002-110174) (Patent Document 8) JP-A-2002-146018 (Patent Document 9) WO02/081547 (Patent Document 10) W02002/08 82 1 9 (Patent Document 11) W02004/ 024796 (Non-Patent Literature) 1) Polymer Proceedings Vol. 59, Νο·8, 460 ～ 4 7 3 (Non-Patent Document 2) Journal of Polymer Science: Part A : Polymer Chemistry, Vol. 34 ' 2421 - 2438 (1996) [Summary of the Invention The object of the present invention is to provide a solid polymer electrolyte having excellent ion conductivity and oxidation resistance, and a solid polymer electrolyte composed of the solid polymer electrolyte and a polymer having ion conductivity. Any of the things, such as 200903890 A polymer electrolyte membrane, a membrane/electrode assembly using the polymer electrolyte membrane, and a fuel cell using the membrane/electrode assembly. In order to solve the problem, the inventors of the present invention have repeatedly focused on the above-mentioned problems and found that a solid polymer electrolyte having a rigid heterocyclic polymer having a specific structure as a component is found. A solid polymer electrolyte composition composed of an electrolyte and a polymer having ion conductivity can solve the above-mentioned 丨Η shape. The constitution of the present invention is shown below. A solid polymer electrolyte obtained by 100 parts by mass of a rigid heterocyclic polymer and 0.1 to 10 parts by mass of an acid, wherein 'the above-mentioned rigid heterocyclic polymer is selected from the following formula (I) And (II)

-9- 200903890 ο

/ΥΊ

At least one repeating unit of the group represented by the repeating unit, and the following formula (III) 0

Ar1

(III) (However, in the above formulae (I) to (III), Ar1 is selected from the group consisting of p-phenylene, m-phenylene, 2,6-naphthalenediyl, 4,4'-biphenyl, 4,4' - one or more groups of sulfonyldiphenylene; in the above formula (III), Ar2 is selected from the group consisting of p-phenylene, m-phenylene, 3,4'-oxydiphenylene, 4,4'-oxygen a repeating unit represented by a bisphenylene, a 4,4'-biphenylene or a 4,4'-sulfonyldiphenylene group, and the formula (I), The copolymerized molar ratio (III) / ((I) + (II)) of the repeating units of II) and (III) is OS (111) / ((I) + (II) ) $5, and at 0.5 g / The specific viscosity of the sulfuric acid solution having a concentration of 100 ml measured at 25 ° C is 0.05 to 100 MPa / g; and the above acid is at least the acid selected from the group consisting of phosphoric acid, polyphosphoric acid, sulfuric acid and methanesulfonic acid. -10-200903890 2. A solid polymer electrolyte membrane in which the solid polymer electrolyte of the above 1 is formed into a film having a thickness of 10 to 200 μm. A solid polymer electrolyte composition comprising the solid polymer electrolyte of the above 1 and a polymer having ion conductivity. 4. The solid polymer electrolyte composition according to the above 3, wherein the solid polymer electrolyte and the polymer having ion conductivity are each in the form of a film and are a laminate of the same. 5-A solid polymer electrolyte composition according to the above 3 or 4, wherein the polymer having ion conductivity is a perfluorocarbonsulfonic acid resin. 6- A film/electrode assembly characterized in that a catalyst electrode is provided on both surfaces of the solid polymer electrolyte membrane of the above 2 or the solid polymer electrolyte composition of the above. A fuel cell characterized by having a membrane/electrode assembly as described above. Advantageous Effects of Invention According to the present invention, it is possible to obtain an excellent oxidation resistance such as SMMΜ for fuel cell, water electrolysis, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrator, humidity sensor, gas sensor, etc. A high-durability solid stomach & m m mass or a composition thereof, and a fuel cell using the polymer electrolyte or a composition thereof. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Further, unless otherwise specified, the number of -11 - 200903890 ppm or % is the mass basis. (Rigid-straight heterocyclic polymer) The rigid heterocyclic polymer used in the present invention is selected from the following formulas (I) and (II)

(II) at least one repeating unit of the group represented by the repeating unit, and the following formula (III)

Ar

(III) (However, in the above formulae (I) to (III), Ar1 is selected from the group consisting of p-benzoene, m-phenylene-12-200903890, 2,6-naphthalenediyl, 4,4'-biphenylene, One or more groups of 4,4,-sulfonyldiphenylene; in the above formula (III), Ar2 is selected from the group consisting of p-phenylene, m-phenylene, 3,4'-oxydiphenylene, and 4, a repeating unit represented by 4'-oxydiphenylene, 4,4'-biphenylene, 4,4 or sulfonyldiphenylene), and the formula (I) The co-polymerization molar ratio (ΠΙ ) / ( ( 1 ) + (II)) of the repeating units of (II) and (III) is OS (111) / ( (I) + (II) ) S5, and The specific viscosity of the sulfuric acid solution having a concentration of 0.5 g/100 ml measured at 25 ° C is 0.05 to 1 〇〇 dl / g, preferably 0.1 to 50 dl / g, more preferably 1 to 1 Odl / g ° The above-mentioned copolymerized molar ratio (III) / ((I) + (Π)) is preferably 0 or more and 1 or less, more preferably 〇 or more and 0.5 or less. The solid polymer electrolyte of the present invention is a mass fraction of the above-mentioned rigid heterocyclic polymer of 10 〇 and at least one acid strontium selected from the group consisting of phosphoric acid, polyphosphoric acid, sulfuric acid, and a sulphuric acid, and 1 to 100 parts by mass. Adult. The acid is added to the molded body to improve the conductivity, and the content of the acid in the solid polymer electrolyte is preferably 0.5 to 50 parts by mass, more preferably 1.0 to 100 parts by mass based on the rigid heterocyclic polymer. 30 parts by mass, and more preferably 3.0 to 20 parts by mass. (Manufacturing Method) The rigid heterocyclic polymer of the group consisting of at least one repeating unit selected from the group consisting of the repeating units represented by the above formulas (1) and (π) is represented by the following formula (A) -13- 200903890 ο ο

X

Ar1

(A) (Ar1 in the formula (A) is selected from the group consisting of p-benzoene, m-phenylene, 2,6-naphthalenediyl, 4,4-biphenylene, 4,4'-sulfonylbiphenylene More than one. The X in the formula (A) is a group represented by OH, a halogen atom or OR, wherein R represents an aromatic dicarboxylic acid represented by a monovalent aromatic group having 6 to 20 carbon atoms. a compound, and at least one selected from the group consisting of the following formula (B) or (C)

(C) NH, a heterocyclic aromatic diamine and its hydrochloride, sulfate, phosphate group, and the following formula (D) H2N, /NH2 \Ar2 (D) (Formula D Ar2 is selected from the group consisting of p-phenylene, m-phenylene, 3,4'-oxydiphenylene, 4,4'-oxydiphenylene, 4,4'-biphenylene, 4,4'- The aromatic diamine represented by one or more of the sulfonyl diphenylenes or the hydrochlorides, sulfates, and phosphates thereof can be suitably obtained. -14- 200903890 The aromatic diphthalic acid ring represented by the above formula (A), that is, Ar1 in the formula (A) is selected from the group consisting of p-benzoquinone, m-base, 4,4,-biphenylene, and 4, 4,-sulfonyldiphenylene 1 Among them, p-phenylene, m-phenylene, and 2,6-naphthalene diyl are particularly preferred. Further, various dicarboxylic acids other than the above formula (A) which are improved in the properties of the obtained polymer are, for example, copolymerized. The aromatic dioxane atom represented by the above formula (A) is preferred, and the aromatic group of X = C1 is preferred. The aromatic diamine compound represented by the above formula (D), that is, Ar2 in the formula (D) is selected from the group consisting of p-phenylene, m-phenylene, 4,4,-oxydiphenyl, 4, 4' One or more bases of biphenylene and phenylene, among which 'p-phenylene 3,4,-oxydiphenylene is preferred, and p-phenylene is particularly preferred. Further, 'the purpose of the nature of the polymer' may be other than the above formula (A), for example, 1,4 -diaminonaphthalene, anthracene, 5-diaminonaphthalene, 2,6-diaminonaphthalene, 2 ,7-Diaminonaphthalene, 2,5-diaminediaminopyridine, 3,5-diaminopyridine, 3,3'-aminochlorobenzidine, 3,3'-diaminodiphenyl ether The copolymerization 1 is carried out, and a compound having a combination of an amine group and a carboxyl group, for example, 'for the purpose of improving the properties of the obtained polymer, is copolymerized. The solvent used in the polymerization is not particularly limited to a compound having two or more aromatic groups and 2,6-naphthalene, and is preferably a compound such as adipic acid or X. The halogenated carboxylic acid chloride is an aromatic ring, 3,4'-oxy 4,4'-sulfonyl di, m-phenylene, and various diamines, 1,8- The diamino group is steep, 2,6-biphenyl, 3,3·-diπ°, and the molecular aminobenzoic acid can also be dissolved as the raw material monomers (A) and (B) of the above -15-200903890 And (C), and (D)' and substantially non-reactive with them, and preferably any polymer having a viscosity of at least i.0 or more, more preferably more than 1.2 or more. A solvent. For example, Ν, Ν, Ν', Ν'-tetramethyl urea (TMU), hydrazine, hydrazine-dimethylacetamide (DMAC), hydrazine, hydrazine-diethyl acetamide (DEAC), Ν,Ν-dimethylpropanamide (DMPR), hydrazine, hydrazine-dimethylbutyramine (ΝΜΒΑ), hydrazine, hydrazine-dimethylisobutylamine (ΝΜΙΒ), Ν-methyl-2- Pyrrolidone (ΝΜΡ), Ν-cyclohexyl-2-pyrrolidone (NCP), Ν-ethylpyrrolidone-2 ( ΝΕΡ ), Ν-methyl decylamine (NMC), hydrazine, hydrazine-dimethyl ketone Oxyacetamide, Ν-ethenylpyrrolidine (NARP), Ν-ethenylpiperidine, Ν-methylpiperidone-2 (NMPD), hydrazine, Ν'-dimethylethylene urea, hydrazine , hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, phenol, hydrazine, hydrazine, phenol, dimethyl hydrazide a phenolic solvent such as p-cresol or 2,4-dichlorophenol or a mixture thereof. Preferred solvents among these are hydrazine, hydrazine-dimethylacetamide (DMAC), and hydrazine-methyl-2-pyridone (Ν Μ 。 ). In this case, it is also possible to add an appropriate amount of a well-known inorganic salt before, during, or at the end of the polymerization in order to exhibit solubility. Examples of such an inorganic salt include lithium chloride and calcium chloride. The production of the polymer is carried out in the same manner as in the above-mentioned solvent in which the above monomers (A), (?), (C) and (D) are dehydrated, and a solution of a general polyamine. In this case, the reaction temperature is preferably 8 (TC or less, preferably 60 ° C or lower. Further, the concentration at this time is preferably about 1 to 20% by weight as the monomer concentration. -16 - 200903890 In the present invention, a trialkylsulfonium alkyl chloride can be used for the purpose of high polymerization degree of the polymer. Further, in the reaction of an aromatic dicarboxylic acid compound and a diamine which are generally used, a hydrogen chloride such as hydrogen chloride is trapped. The acid may be an aliphatic or aromatic amine or a quaternary ammonium salt. In order to obtain the wholly aromatic polyamine of the invention, in the above organic solvents '(B), (C) and (D) The total amount of the diamine to be used is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, based on the ratio of the molar amount of the aromatic dicarboxylic acid compound represented by (A). It is preferably a wholly aromatic polyamine. In this wholly aromatic polyamine, the end of the sealing polymer can be suitably used. In the case of sealing with an end sealant, benzamidine as its terminal sealant can be cited. Chloride, phthalic anhydride and its substitutes, hexahydrophthalic anhydride and its substitutes, succinic anhydride The substituted product; the aniline as the amine component and the substituted product thereof, but not limited thereto. The solid molecular electrolyte of the present invention is a rigid heterocyclic polymer, and at least one selected from the group consisting of phosphoric acid, polyphosphoric acid, sulfuric acid, A method of adding the acid of the group of methanesulfonic acid. The method of adding the acid to the rigid heterocyclic polymer can be added to the coating material, added during solidification, added after washing, or washed with water and dried. (Solid polymer electrolyte and film forming method thereof) The solid polymer electrolyte of the present invention is preferably a film having a thickness of 10 to 200 μm. As a film forming method, (i) casting method or Ii) Pressure -17- 200903890 is preferred. The thickness of the electrolyte membrane is preferably 30 to ΙΟΟμιη. It is better to obtain a film thickness that is more resistant to practical use than 1 〇μπι; The power generation performance is preferably less than 200 μηι. The thickness of the film is controlled by the solution casting method, and can be controlled by the solution concentration or the coating thickness on the substrate; in the case of the pressing method, It is controlled by the concentration of the solution or the pressure of the pressing. (Casting method) The casting method refers to casting a polymer solution (dope) containing a rigid heterocyclic polymer and a solvent onto a substrate such as a glass plate. A method of removing a solvent to form a film. The solvent 'is a solution of a rigid heterocyclic polymer, and if it is removed later, it is not particularly limited, and N,N-dimethylacetamide, N,N-dimethyl can be used. An aprotic polar solvent such as a genus of a genus, a genus, a N-methyl-2 - anthraquinone, a hexamethyl phosphon amide, or a polyphosphoric acid or methanesulfonic acid. A strong acid such as sulfuric acid or trifluoroacetic acid. These solvents are used in a range of possible amounts. Further, as a method for improving the solubility, a Lewis acid such as lithium bromide, lithium chloride or aluminum chloride may be added to an organic solvent as a solvent. The concentration of the rigid heterocyclic polymer in the coating is preferably from 0.1 to 8% by mass. If it is too low, the formability is deteriorated, and if it is too high, the workability is deteriorated. In the solution casting method, a film having a low degree of orientation in the in-plane direction can be obtained by setting the concentration of the rigid heterocyclic polymer in the coating to a predetermined range. As the casting method, a casting coating such as a doctor blade, a bar coating -18-200903890, or an applicator is used for the support, and after the solvent is washed, a method of drying the film is preferred. The drying temperature can be 〇 〜 2 0 0 ° C, preferably 20 ° C ~ 1 50 ° C, more preferably 5 0 t: ~ 8 0 ° C. (Pressing method) The rigid straight heterocyclic polymer is a film having high crystallinity and being formed into a film by general extrusion without obtaining an isotropic property in the in-plane direction. Therefore, a film can be formed by applying a ruthenium pressure to a substrate containing a rigid heterocyclic polymer and a solvent, and an isotropic film can be obtained in the in-plane direction. The solvent is the same as the casting method. The concentration of the rigid heterocyclic polymer in the coating is preferably from 1 to 30% by mass, more preferably from 0 to 5 to 8% by mass. The pressure system is preferably 〇.〇1 to lOOOMPa, more preferably 1 to 10 MPa. It is preferable to perform heating at the time of film formation. The heating temperature is preferably from 100 to 300 ° C, more preferably from 130 to 250 ° C. (Particles) Further, the solid polymer electrolyte of the present invention may be in the form of particles in addition to the above-mentioned film shape. Examples of the method for producing the pellets include a compression roll method, a briquetting method, and a making tablet. More specifically, it is preferred to carry out granulation using a tablet molding machine or a compression molding machine. (Polymer having ion conductivity) The polymer having ion conductivity used in the present invention may, for example, be a single polymer having a monomer such as an ion exchange group of _S03H, and a total of -19-200903890 A polymer or a random copolymer such as a perfluorocarbonsulfonic acid resin or a polyetheretherketonesulfonic acid resin having an ion conductivity introduced by post-treatment with an -S〇3H-based ion exchange group. Among them, a high molecular ion having a ionic conductivity is preferably a perfluorocarbon sulfonic acid resin. (Solid polymer electrolyte composition composed of a solid polymer electrolyte and a polymer having ion conductivity) The solid polymer electrolyte composition of the present invention is a solid polymer electrolyte containing the above-mentioned rigid heterocyclic polymer and It is made of a polymer having ion conductivity. The solid polymer electrolyte which is a mixture of the solid polymer electrolyte and the polymer having ion conductivity may be a layer formed by forming the solid polymer electrolyte into a film and ion conduction. The polymer is a laminate of two layers formed by a film. In the case of the mixture, the polymer having ion conductivity is 1 to 800 parts by mass, preferably 3 to 30,000 parts by mass, and further preferably 5 to 100 parts by mass, based on 100 parts by mass of the rigid heterocyclic polymer. good. In the case of a laminate, a layer made of a polymer having ion conductivity is preferably provided on one side or both sides of a layer formed of a rigid heterocyclic polymer. The lamination method may, for example, be a known pressing method, a hot pressing method, a casting method, a spin coating method, a lamination method, or the like, but is not limited thereto. (Film/Electrode Bonding Body) The membrane/electrode assembly (Membrane Electrode Assembly hereinafter referred to as MEA) of the present invention has a catalyst electrode on the surface of two to 20-200903890 of the electrolyte membrane of the present invention. The catalyst electrode is a particle that carries the catalyst metal in the conductive material. As the catalyst metal, any metal which promotes the oxidation reaction of hydrogen and the reduction reaction of oxygen may be used. For example, platinum, gold, silver, palladium, rhodium, iridium, iridium, iron, cobalt, nickel, chromium, tungsten, manganese, vanadium, or alloys thereof may be mentioned. In particular, lead is used in most cases. The particle diameter of the catalytic metal is generally 10 to 300 angstroms (1 to 30 nm). The conductive material is preferably an electron conductive material. Examples of the conductive material include various metals and carbon materials. Examples of the carbon material include carbon black such as furnace black, channel black, and acetylene black, activated carbon, and graphite. These can be used individually or in combination. The loading amount of the catalyst metal is preferably 0.01 to 10 mg/cm 2 in a state of being formed into an electrode. A method of supporting a catalytic metal in the conductive material, wherein the catalyst metal is deposited on the surface of the conductive material by a reduction method, or the catalyst metal is suspended in a solvent to coat the surface of the conductive material. Method, etc. (Fuel Cell) The solid polymer electrolyte of the present invention is preferably used in a fuel cell. In the fuel cell of the present invention, a current collector in which a fuel flow path or a oxidant flow path called a separator is formed on the outer side of the membrane/electrode assembly is a single cell. Further, a plurality of such unit cells are laminated by a cooling plate or the like. The fuel cell is composed of a plurality of such unit cells, wherein a current collector that forms a grooved flow of a fuel flow path or an oxidant flow path called a separator on the outer side of the membrane/electrode assembly is a single cell unit. It is formed by laminating a cooling plate or the like into 200903890. When the fuel cell is operated at a high temperature, it is desirable to increase the catalytic activity of the electrode and reduce the electrode overvoltage. However, since the electrolyte membrane has no effect due to the absence of moisture, it is necessary to operate at a temperature at which moisture can be managed. The operating temperature of the fuel cell is preferably in the range of room temperature to 10 (TC). [Embodiment] Hereinafter, the present invention will be more specifically described by way of Examples and Comparative Examples, but the present invention is not given Further, each of the measured oxime in the following examples is obtained by the following method. [Special viscosity] Concentrated sulfuric acid will be used at a polymer concentration of g 5 g / dl at 30 ° C The relative viscosity (T!re|) of the measurement was determined according to the following formula.

Ίίη„= ( 1ηηΓ6ΐ ) / C (Inh indicates specific viscosity, 1Uel indicates relative viscosity, C indicates concentration) [Ion Conductivity Measurement] The electrolyte membrane of the present invention uses an electrochemical impedance measurement device (Solartron, SI1287) In the field of frequency 〇_iHz to 65 kHz, the impedance measurement in the thickness direction of the film is performed to measure the ion conductivity. Further, in the above measurement, the electrolyte membrane is stored under a water vapor atmosphere, and is stored at -22-200903890 at 75 ° C. [Oxidation Resistance Test] The electrolyte membrane of the present invention is immersed in 2 liters of hydrazine sulfate 7-hydrate containing 1.9 mg of 30% hydrogen peroxide water to 2 (Fenton reagent heated by rC) (Fenton's reagent) (40 ppm of iron) was used to determine the time during which the electrolyte membrane was dissolved in the Fenton's reagent. [Method for measuring the content of phosphorus atoms] The sample was taken in a wet decomposition vessel with reflux cooling, and concentrated sulfuric acid was added. Heating 'so that the sample does not fly loosely and slowly drop the nitric acid to completely decompose the organic matter. After cooling, add pure water and constant volume in a white transparent glass container. Phosphorus atom was quantified by ICP emission spectrometry. Reference Example 1 (Polymerization of Polymer) Calcium chloride 1 4 · 24 parts by mass was dried under a nitrogen stream in a flask at 250 k t for 1 hour, and the temperature in the flask was maintained. After returning to room temperature, 150 parts by mass of N-methyl-2-pyrrolidone (NMP) was added, and 5 (6)-amino-2-(4-aminophenyl)benzimidazole (cas) was dissolved. Reg_ no. 7621—86— 5) 10 parts by mass of 2.066 parts by mass of p-phenylene diamine. This solution was stored in 〇 ° C by external cooling, and 2.93 parts by mass of terephthalic acid chloride was added. The reaction was carried out at 0 ° C for 1.5 hours and 50 ° C for 3 hours, and 4.720 parts by mass of calcium hydroxide was added to obtain a polymer coating. The specific viscosity of the obtained polymer was 4.9-200903890 degrees was 4.9. (Production of cast film) The polymer paint obtained in Reference Example 1 was spread on a glass by a doctor knife, solidified in 85% phosphoric acid for 24 hours, washed with water for 1 hour, and dried at 120 ° C. An electrolyte membrane having a thickness of 200 μm was produced, and the content of the phosphorus atom was 5% by mass, and the content of phosphoric acid was 15.8% by mass. The ionic conductivity and oxidation resistance of the cast film were shown in Table 1. Example 2 (Production of laminate) Example of sandwiching both sides of a Nafion (registered trademark) film manufactured by Du Pont Co., Ltd. having a thickness of 170 μm The film obtained in 1 was measured for ion conductivity and oxidation resistance. The results are shown in Table I. Reference Example 2 (Polymerization of Polymer) 15 parts by mass of calcium chloride was dried under a nitrogen stream in a flask at 250 ° C for 1 hour, and after the temperature in the flask was returned to room temperature, N-A was added. Base-2 - pyrrolidone 300 parts by mass. 10 parts by mass of 5 (6)-amino-2-(4-aminophenyl)benzimidazole (cas. reg. no. 7621-86-5) was dissolved. This solution was stored by external cooling at 〇 ° C 'Addition of terephthalic acid chloride 9.0 5 2 8 parts by mass, and allowed to react at 〇 ° C for 3 hours, 50 ° C for 3 hours, and added calcium hydroxide 3 · 3 03 parts by mass 'to find a polymer coating. The specific viscosity of the obtained polymer was 4.3 ° -24 - 200903890. Example 3 (Production of cast film) The polymer paint obtained in Reference Example 2 was spread on a glass by a doctor blade and solidified in 8 5 % phosphoric acid. After the hour, the mixture was washed with water for 1 hour, and dried at i 2 ° C to prepare an electrolyte membrane having a film thickness of 40 μm. The content of the phosphorus atom was 6% by mass. The content in terms of phosphoric acid was 19% by mass. The measurement results of the physical properties of the cast film obtained are shown in Table 1. Example 4 (Production of laminate) The film obtained in Example 3 was coated on both sides of a Nafi on (registered trademark) film manufactured by Du Pont Co., Ltd. having a film thickness of 170 μm to measure ion conductivity and oxidation resistance. The results are shown in Table 1. Example 5 (Production of membrane/electrode assembly (MEA)) Using the cast film (electrolyte membrane) obtained in Example 3, the electrode/electrolyte membrane/attached by the catalyst was prepared by hot pressing. A laminate formed by the composition of the electrodes of the catalyst. The catalyst-attached electrode is a catalyst layer which is an electrode substrate made of a carbon paper Teflon treated product having a thickness of 4 μm and a platinum supporting the catalyst at 1 mg/cm 2 . The carbon carrier carried by the base weight carrier. The hot pressing conditions were a pressure of 10 0 kg/cm 2 (9_8 MPa) and a temperature of 150 Å.匚, hold time is 3 minutes. Thereby, it is possible to produce -25-200903890 Μ E A which is excellent in the bonding property between the electrolyte and the electrode of the catalyst. Example 6 (Evaluation of power generation characteristics) Using the Μ E A produced in Example 5, the power generation characteristics were observed under the following conditions. (1) Cell unit for evaluation fuel cell (ce 11 ) 5 cm 2 gas flow rate portion, graphite plate as a separator, and battery unit of Electrochem Co., Ltd. made of gold-plated steel sheet as a current collector (single cell). (2) Measurement conditions • Hydrogen: Supply rate: 50 ml/min • Mixed gas: Oxygen/nitrogen (20% / 80%) Supply speed: 220 ml / min • Humidification simultaneously with hydrogen and mixed gas. • Battery temperature: measured at 40, 50, 60, 70 °C. Table 2 shows an overview of the output characteristics of each temperature. Table 1 Ion Conductivity Measurement (S/cm) Oxidation Resistance Test (minutes) Example 1 0.0008 Insoluble Example 2 0.007 Insoluble Example 3 0.001 Insoluble Example 4 0.009 Insoluble -26- 200903890 Table 2 Measurement Temperature Rc) Output density (mW/cm2) 40 5.6 50 4.1 60 12.1 70 3.3

Claims (1)

200903890 X. Patent application scope 1. A solid polymer electrolyte which is composed of 100 parts by mass of a rigid heterocyclic polymer and 0.1 to 100 parts by mass of an acid, wherein the above-mentioned rigid heterocyclic polymer is selected from the group consisting of (I) and (II) Η Ν Ν ΝΗ ο /ΤΊ Η (II) at least one repeating unit of the group represented by the repeating unit, and the following formula (III) Ο Ο (However, in the above formulae (I) to (III), Ar1 is selected from the group consisting of p-phenylene, m-Benzene-28-200903890, 2,6-naphthalenediyl, 4,4'-biphenyl, 4,4 One or more groups of '-sulfonyldiphenylene; in the above formula (111), Ar2 is selected from the group consisting of p-phenylene, m-benzopyrene, 3,4-oxydiphenylene, 4,4'- a repeating unit represented by one or more of oxydiphenylene, 4,4'-biphenylene, and 4,4'-sulfonyldiphenylene), and the formula (1), The copolymerization molar ratio (in) / ( ( I ) + (Π)) of the (Π) and (in) repeating units is OS (111) / ( (I) + (II) ) $5, and at 0.5 g The specific viscosity of the sulfuric acid solution at a concentration of / 1 0 0 m 1 measured at 25 ° C is 0.05 ～1 00 dl / g; the above acid is selected from the group consisting of phosphoric acid, polyphosphoric acid 'sulphuric acid and methanesulfonic acid At least 1 acid. 2. A solid polymer electrolyte membrane which is a solid polymer electrolyte having a thickness of 1 〇 2 〇〇 η ι · · · · · · · · · · · · · · · · · · · · It is made up of a solid polymer electrolyte of the first application of the patent scope and a polymer having ion conductivity. 4. The solid polymer electrolyte composition according to claim 3, wherein the solid polymer electrolyte and the polymer having ion conductivity are each in the form of a film and are a laminate of the same. 5. The solid-oxymolecular electrolyte composition of the third or fourth aspect of the patent application, wherein the polymer having ion conductivity is a perfluorocarbonsulfonic acid resin. 6. The film/electrode assembly is characterized in that it is a solid polymer electrolyte membrane according to item 2 of the application patent No. -29-200903890 or a solid polymer electrolyte composition according to claim 5 of the patent application. A catalyst electrode is disposed on the electrode. A fuel cell characterized by having a membrane/electrode assembly as claimed in claim 6 of the patent application. -30- 200903890 VII. (1) The designated representative circle of this case is: None (2). The symbolic representation of the symbol of the representative figure is as follows: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: