JP4979243B2 - Polymer electrolyte membrane, method for producing the same, and fuel cell - Google Patents

Description

  The present invention relates to a polymer electrolyte membrane, a manufacturing method thereof, and a fuel cell, and more particularly to a polymer electrolyte membrane excellent in thermal characteristics and mechanical stability and a fuel cell employing the polymer electrolyte membrane.

  A fuel cell is a device that produces electric energy by electrochemically reacting fuel and oxygen, and not only supplies power for industrial, household, and vehicle driving, but also small electric / electronic products, It is also applicable to power supply for portable devices.

  Depending on the type of electrolyte used, the fuel cell may be a polymer electrolyte fuel cell (PEMFC), a phosphoric acid fuel cell (PAFC), or a molten carbonate fuel cell (MOFC). MCFC) and solid oxide fuel cell (SOFC). Depending on the electrolyte used, the operating temperature of the fuel cell, the material of the components, and the like change.

  The fuel cell uses an external reforming type in which fuel is converted to a hydrogen-enriched gas via a fuel reformer and then supplied to the anode through a fuel reformer, and fuel in a gas or liquid state is directly supplied to the anode. The fuel can be classified into a direct fuel supply type or an internal reforming type.

  A typical example of the direct fuel supply type is a direct methanol fuel cell (DMFC). DMFC generally uses a methanol aqueous solution as a fuel and a hydrogen ion conductive polymer electrolyte membrane as an electrolyte. Therefore, DMFC also belongs to PEMFC.

  PEMFC can realize high power density even if it is small and light. Furthermore, the use of PEMFC simplifies the configuration of the power generation system.

  The basic structure of a PEMFC generally comprises an anode (fuel electrode), a cathode (oxidant electrode), and a polymer electrolyte membrane disposed between the anode and cathode. The anode of the PEMFC is equipped with a catalyst layer for promoting the oxidation of the fuel, and the cathode of the PEMFC is equipped with a catalyst layer for promoting the reduction of the oxidant.

  As the fuel supplied to the anode of the PEMFC, hydrogen, a hydrogen-containing gas, a mixed vapor of methanol and water, an aqueous methanol solution, or the like is generally used. The oxidant supplied to the PEMFC cathode is typically oxygen, oxygen-containing gas or air.

  In the anode of the PEMFC, the fuel is oxidized to generate hydrogen ions and electrons. Hydrogen ions are transferred to the cathode via the electrolyte membrane, and electrons are transferred to the external circuit (load) via the conductive wire (or current collector). In the cathode of the PEMFC, hydrogen ions transmitted through the electrolyte membrane and electrons and oxygen transmitted from an external circuit are combined through a conductive wire (or current collector) to generate water. At this time, the movement of electrons via the anode, the external circuit, and the cathode is just electric power.

  In PEMFC, the polymer electrolyte membrane serves not only as an ionic conductor for the transfer of hydrogen ions from the anode to the cathode, but also as a separator that blocks the mechanical contact between the anode and the cathode. Therefore, the characteristics required for polymer electrolyte membranes are excellent ionic conductivity, electrochemical safety, high mechanical strength, thermal stability at operating temperature, and ease of thinning.

  As a material for the polymer electrolyte membrane, generally, a perfluorosulfonic acid polymer having a main chain composed of fluorinated alkylene and a side chain composed of a fluorinated vinyl ether having a sulfonic acid group at the terminal (example: Polymer electrolytes such as Nafion (a trademark of Dupont) are used. Such a polymer electrolyte membrane exhibits excellent ionic conductivity by containing a suitable amount of water.

  However, such an electrolyte membrane loses its function as an electrolyte membrane due to a serious decrease in ionic conductivity due to water loss due to evaporation at an operating temperature of 100 ° C. or higher. Therefore, it is almost impossible to operate a PEMFC using such a polymer electrolyte membrane under normal pressure and at a temperature of 100 ° C. or higher. Therefore, the conventional PEMFC has been mainly operated at a temperature of 100 ° C. or lower, and about 80 ° C. as a non-limiting example.

  In order to raise the operating temperature of PEMFC to 100 ° C or higher, there are methods such as attaching a humidifier to PEMFC, operating PEMFC under pressure, or using polymer electrolyte that does not require humidification. It was proposed.

  When the PEMFC is operated under pressurized conditions, the boiling point of water increases, so that the operating temperature can be increased. For example, if the operating pressure of the PEMFC is 2 atm, the operating temperature can be increased to about 120 ° C. However, if a pressurization system is applied or a humidifier is attached, not only the size and mass of the PEMFC will be greatly increased, but also the overall efficiency of the power generation system will be reduced. As a result, in order to maximize the utilization range of PEMFC, there is an increasing demand for “non-humidified polymer electrolyte membranes”, that is, polymer electrolyte membranes that exhibit excellent ionic conductivity without being humidified.

  An example of a non-humidified polymer electrolyte membrane is introduced in Patent Document 1. The document discloses a material such as polybenzimidazole doped with polybenzimidazole, sulfuric acid or phosphoric acid as a non-humidified polymer electrolyte.

Japanese Patent Laid-Open No. 11-503262

  Therefore, the present invention has been made in view of such problems, and an object of the present invention is to provide a polymer electrolyte membrane that is stable at high temperature but has excellent mechanical strength and excellent ionic conductivity even in a non-humidified state, and its It is an object of the present invention to provide a manufacturing method and a fuel cell provided with the polymer electrolyte membrane.

  In order to solve the above problems, according to a first aspect of the present invention, a porous polymer matrix and ions formed on the outer surface of a single fiber of the porous polymer matrix and inside the pores of the polymer matrix. A polymer electrolyte membrane comprising a conductive polymer coating membrane is provided.

Ion-conducting polymer of the ion conducting polymer coating membrane, Ru polymerization product der the ion conducting polymeric compound and a crosslinking agent.

  The ion conductive polymerizable compound is selected from vinyl sulfonic acid, styrene sulfonic acid, sulfonyl acrylate, acrylic resin having an acidic functional group at the terminal, C1 to C20 alkylamine, and vinyl monomer having a basic functional group at the terminal. One or more selected, and the mass average molecular weight of the ion conductive polymerizable compound may be 1000 g / mol or less.

  The acrylic resin having an acidic functional group at the terminal is phosphorus monoacrylate or phosphorus diacrylate, and the alkylamine is 2- (tert-butyl-methylamino) ethyl acrylate, N-tert-butyl. Diethanolamine or N- (1-cyanocyclohexyl) -1-N-methylbutyramide, the vinyl monomer having a basic functional group at the terminal is vinylpyridine, vinylpyrrolidone, polyethyleneimine, or 1-vinylimidazole. One or more selected from may be used.

  The ion conductive polymerizable compound has at least one functional group selected from a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, an imide group, a sulfonimide group, a sulfonamide group, and a hydroxyl group at the terminal, and a head portion. And the ion-conducting polymerizable compound may have a mass average molecular weight of 10,000 g / mole or less.

  The cross-linking agent may be one or more selected from hexyl acrylate, butyl acrylate, trimethylolpropane triacrylate, poly (ethylene glycol) methacrylate, poly (ethylene glycol) dimethacrylate, allyl acrylate, and divinylbenzene. Good.

  The ion conductive polymer coating film may be obtained by finely coating a composition containing an ion conductive polymerizable compound and a crosslinking agent and then polymerizing the fine particle coated composition.

  A plasticizer may be further added to the composition.

  The plasticizer may be one or more selected from the group consisting of poly (ethylene glycol) methyl ether acrylate and polyallyl ether.

  The porous polymer matrix may be a nonwoven fabric made of one or more selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, and polyethylene.

  The porous polymer matrix may have a thickness of 10 to 150 μm, and the porosity per area of the porous polymer matrix may be 30 to 90%.

  The ion conductive polymer coating film may have a thickness of 1 to 10 μm.

  In order to solve the above problems, according to a second aspect of the present invention, a composition containing an ion conductive polymerizable compound and a cross-linking agent is used on a porous polymer matrix to form a vacuum deposition coating of a fine particle coating. And a polymer comprising the ion conducting polymer coating film formed on the outer surface of the single fiber of the porous polymer matrix and inside the pores of the polymer matrix. A method for producing a polymer electrolyte membrane is provided which includes a step of obtaining an electrolyte.

  The fine particle coating may be performed by a flash evaporation method.

  The composition may further include 20 to 200 parts by mass of a plasticizer based on 100 parts by mass of the ion conductive polymerizable compound.

  The plasticizer may be one or more selected from the group consisting of poly (ethylene glycol) methyl ether acrylate and polyaryl ether.

  The polymerization reaction may be performed by irradiating light, using an electron beam, or applying heat.

  The ion conductive polymerizable compound is selected from vinyl sulfonic acid, styrene sulfonic acid, sulfonyl acrylate, acrylic resin having an acidic functional group at the terminal, C1 to C20 alkylamine, and vinyl monomer having a basic functional group at the terminal. One or more selected, and the mass average molecular weight of the ion conductive polymerizable compound may be 1000 g / mol or less.

  The acrylic resin having an acidic functional group at the terminal is phosphorus monoacrylate or phosphorus diacrylate, and the alkylamine is acrylic acid 2- (tert-butyl-methylamino) ethyl ester, N-tert-butyldiethanolamine. Or N- (1-cyanocyclohexyl) -1-N-methylbutyramide, and the vinyl monomer having a basic functional group at the terminal is vinylpyridine, vinylpyrrolidone, polyethyleneimine, or 1-vinylimidazole. It may be one or more selected.

  The ion conductive polymerizable compound has at least one functional group selected from a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, an imide group, a sulfonimide group, a sulfonamide group, and a hydroxyl group at the terminal, and a head portion. And the ion-conducting polymerizable compound may have a mass average molecular weight of 10,000 g / mole or less.

  The cross-linking agent may be one or more selected from hexyl acrylate, butyl acrylate, trimethylolpropane triacrylate, poly (ethylene glycol) methacrylate, poly (ethylene glycol) dimethacrylate, allyl acrylate, and divinylbenzene. Good.

  The crosslinking agent may be 25 to 300 parts by mass based on 100 parts by mass of the ion polymerizable compound.

  In order to solve the above problems, according to a third aspect of the present invention, there is provided a fuel cell comprising a cathode, an anode, and the polymer electrolyte membrane interposed between the cathode and the anode. The

  According to the present invention, a polymer electrolyte membrane, a method for producing the same, and a fuel that have excellent mechanical strength, are not deteriorated by heat even at a temperature of 100 ° C. or higher, and can exhibit excellent ionic conductivity even in a non-humidified state. A battery can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the present specification and drawings, components having substantially the same functional configuration are denoted by the same reference numerals, and redundant description is omitted.

  The polymer electrolyte membrane according to the first embodiment of the present invention includes a porous polymer matrix having excellent mechanical strength and thermal characteristics, and an outer surface of a single fiber (or individual fiber) constituting the polymer matrix. , Having a structure in which an ion conductive polymer coating film obtained by grafting or crosslinking an ion conductive polymerizable compound having various ion conductive (especially hydrogen ion conductive) groups is formed, The polymer matrix has a structure in which an ion conductive polymer coating film is formed on a single fiber or thread inside the pores of the polymer matrix. As described above, the polymer electrolyte membrane according to the present embodiment includes the ion conductive polymer coating film. However, depending on the degree of the ion conductive polymer coating, the polymer electrolyte membrane has a structure in which some pores exist in the polymer matrix. Have.

  Here, if the term “polymer electrolyte membrane” is defined, it means an ionic conductor including a polymer electrolyte matrix impregnated with an ionic medium. In DMFC, the ionic medium is a monomer to be coated, and is a sulfone. This refers to a monomer (Nafion) containing an acid group. In PAFC, the ion medium is phosphoric acid itself, and in the secondary battery system, the ion medium is an ion of an alkali metal such as Li, Na, or K.

  The term “single fiber” as used in the present invention refers to a single fiber or thread having a porous polymer matrix and a web morphology having a pore interior and a three-dimensional structure. Refers to each fiber or thread that comprises

The polymer electrolyte membrane described above is particularly useful as a non-humidified polymer electrolyte membrane, and it has excellent mechanical safety by coating a porous polymer matrix with a thermal safety of 200 ° C or higher with an ion conductive polymer. And high thermal properties. Here, the “non-humidified polymer electrolyte membrane” is a polymer electrolyte membrane that exhibits excellent ionic conductivity without moisture, and has an appropriate ionic conductivity even at temperatures of 100 ° C. or higher under atmospheric pressure. It means a polymer electrolyte membrane that maintains (10 ⁻² S / cm or more).

  The ion conductive polymer is formed by polymerization of an ion conductive polymerizable compound and a composition containing a crosslinking agent.

  The ion conductive polymerizable compound has, at the end, an acidic group such as a sulfonic acid group, a phosphoric acid group or a carboxylic acid group, a basic group such as pyridine, pyrrolidone, imine or imidazole, or an imide group, a sulfonimide group, It has an ion conductive functional group such as a sulfonamide group and a hydroxyl group, and the head portion is composed of a polymerizable bond, for example, an unsaturated bond such as a double bond, a compound having a functional group such as an epoxy. Say. The mass average molecular weight of the ion conductive polymerizable compound is about 10,000 g / mole or less, preferably 100 to 10000 g / mole, more preferably 50 to 2000 g / mole. If the mass average molecular weight exceeds 10,000 g / mole, it is not desirable in terms of conductivity.

  Examples of the ion conductive polymerizable compound include vinyl sulfonic acid, styrene sulfonic acid, sulfonyl acrylate, an acrylic resin having an acidic functional group at the terminal, a C1 to C20 alkylamine, and a vinyl monomer having a basic functional group at the terminal. and so on.

  Examples of the acrylic resin having an acidic functional group at the terminal include, for example, phosphorus monoacrylate or phosphorus diacrylate, and specific examples of the compound having a basic group at the terminal include, for example, vinyl pyridine. , Vinylpyrrolidone, poly (ethyleneimine), 1-vinylimidazole and the like.

  Examples of the alkylamine include acrylic acid 2- (tert-butyl-methylamino) ethyl ester, N-tert-butyldiethanolamine, or N- (1-cyanocyclohexyl) -1-N-methylbutyramide.

  Among the compounds mentioned above, basic compounds such as vinylpyridine, vinylpyrrolidone, and poly (ethyleneimine) have increased hydrophilicity and bind to the polymer that constitutes the polymer matrix, resulting in compatibility with phosphoric acid. Increases the phosphate retention capacity.

  The basic compound as described above is superior to a compound containing an acidic group such as a sulfonic acid group or a carboxylic acid group in terms of phosphate retention capacity.

The cross-linking agent improves the mechanical properties of the polymer electrolyte membrane. As specific examples, for example, hexyl acrylate, butyl acrylate, trimethylolpropane triacrylate (TMPTA), poly (ethylene glycol) methacrylate (PEGMA, H _{2 C = C (CH 3)} -C (= O) - (OCH 2 CH 2) n -OH, n is an integer of 1 to 25), poly (ethylene glycol) dimethacrylate _(PEGDMA, H 2 C = C (CH ₃ ) —C (═O) — (OCH ₂ CH ₂ ) _n —OC (═O) —C (CH ₃ ) ═CH ₂ , n is an integer of 1 to 25), allyl acrylate And divinylbenzene. The content of the crosslinking agent is preferably 25 to 300 parts by mass based on 100 parts by mass of the ion conductive polymerizable compound. If the content of the cross-linking agent is less than 25 parts by mass, the amount of the cross-linking agent is small and the effect of cross-linking is insufficient. If the content exceeds 300 parts by mass, the polymer is excessively cross-linked and hinders proton movement. This is undesirable because the conductivity is low.

In order to increase the flexibility of the polymer electrolyte membrane, a plasticizer may be further added to the above-described ion conductive polymerizable compound and the composition containing the crosslinking agent. As a specific example of such a plasticizer, for example, poly (ethylene glycol) methyl ether acrylate (CH ₂ ═CH—C (═O) O— (CH ₂ CH ₂ O) _m —CH ₃ , m is 1 to integer of 25), polyallyl ether _{(CH 2 = CH- (CH 2} CH 2 O) m -CH 3, m may be mentioned 1 to 25 integer) and the like.

  The content of the plasticizer is preferably 20 to 200 parts by mass based on 100 parts by mass of the ion conductive polymerizable compound. If the content of the plasticizer is less than 20 parts by mass, the effect as a plasticizer is negligible, and if it exceeds 200 parts by mass, the mechanical properties deteriorate, which is not desirable.

  The porous polymer matrix constituting the polymer electrolyte membrane according to the present embodiment is selected from the group consisting of, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polypropylene (PP), and polyethylene (PE). The film has a thickness of 10 to 150 μm and a porosity per area of 30 to 90%, preferably 40 to 80%. If the porosity is less than 30%, the ionomer coating amount is reduced and the conductivity is directly reduced. If the pore is more than 90%, the conductivity is Although improved, there is a characteristic that mechanical properties are relatively lowered.

  In particular, when a porous polymer matrix made of PTFE is used as the porous polymer matrix according to the present embodiment, it is useful for high-temperature polymer electrolyte fuel cells, and is a porous porous matrix such as PVDF and PP. When using a conductive polymer matrix, it is useful for DMFC with reduced methanol crossover.

  In the polymer electrolyte membrane according to the present embodiment, the thickness of the ion conductive polymer coating film formed on the outer surface of the single fiber is preferably 1 to 10 μm, particularly 1 to 3 μm. If the thickness of the coating film is less than 1 μm, the ionomer coating amount is insufficient and the ionic conductivity decreases. If the thickness exceeds 10 μm, the electrolyte film blocks the pores and the conductivity characteristics decrease. This is undesirable.

  Hereinafter, it will be as follows if the manufacturing method of the polymer electrolyte membrane concerning this embodiment is described.

  Fine particle coating is performed using a composition containing an ion conductive polymerizable compound and a crosslinking agent on a porous polymer matrix. Such a fine particle coating method is not particularly limited. As a specific example, the flash evaporation method may be used to coat the composition on only one surface of the porous polymer matrix. It is also possible to coat twice on both sides.

  The coating method using the flash evaporation method will be described in more detail as follows.

  This is a method in which monomer is sublimated at high temperature and ultra-low pressure and sprayed onto the substrate at a time to coat the pores and surface. The thickness of the coating film is adjusted by adjusting the amount of the mixed monomer. Adjust. This coating method is described in U.S. Pat. No. 6,468,595, and this coating method is used in the present invention.

  After the fine particle coating is performed as described above, a polymerization reaction of the composition is performed, and a polymer electrolyte membrane having a coating film made of an ion conductive polymer is formed on the outer surface of a single fiber of a porous polymer matrix. obtain. The fine particle coating method is not particularly limited, but vacuum deposition coating is performed.

  The polymerization reaction can be performed by light, heat, or electron beam. As the light, ultraviolet (UV) is used, and when it is heated, the temperature is maintained at 70 to 350 ° C. Through such a polymerization reaction, a polymerization reaction such as a cross-linking reaction or graft reaction between the ion conductive polymerizable compound and the cross-linking agent occurs, and an ion conductive polymer corresponding to this occurs. As described above, a plasticizer may be further added to the composition.

  The fuel cell according to the present embodiment can be obtained by including the cathode, the anode, and the polymer electrolyte membrane positioned between the cathode and the anode.

  Hereinafter, the present invention will be described with reference to the following examples, but the present invention is not limited to the following examples.

(Examples 1-4)
As the composition of the following Table 1, vinyl pyridine _{(CH 2 = CH-C 5} H 4 N), diacrylate _{(H 2 C = C (CH} 3) -C (= O) - (OCH 2 CH 2) n -OC (═O) —C (CH ₃ ) ═CH ₂ , n is an integer of 1 to 25), acrylate secondary amine (acrylic acid 2- (tert-butyl-methyl-amino) -ethyl ester (CH ₂ ═CH was prepared _{-COO-C 2 H 4 N (} CH 3) n- (CH 3) 3 ion conducting polymeric compound selected from the group consisting of) and compositions TMPTA are mixed. Thereafter, the composition, After flash evaporation on PVDF matrix, PTFE matrix, or Celgard matrix (PE matrix), respectively, this was irradiated with UV for 10 minutes, 10 kV, 1 An in-situ polymerization reaction was performed with an electron beam of 0 mA, and as a result, a polymer of proton conductive polymer vinylpyridine and diacrylate was coated to a thickness of 5 μm on a single fiber of a PVDF matrix. A polymer electrolyte membrane was obtained, and the total thickness of this polymer electrolyte membrane was 23 μm, where the polymer electrolyte membrane was impregnated with 85% phosphoric acid aqueous solution at 80 ° C. for 2 hours to produce a fuel cell. Used at times.

On the other hand, an EFCG-S type electrode manufactured by E-TEK, that is, an electrode having a loading amount of 0.6 mg / cm ² in which 10% by mass of Pt is supported on Toray Carbon Paper TGPH900 was used. In order to impregnate the electrode with phosphoric acid, phosphoric acid was moistened on the electrode and then stored at 120 ° C. for 1 hour under vacuum.

  A fuel cell was completed comprising the electrode and the polymer electrolyte membrane.

  The cell performances of the fuel cells manufactured according to Examples 1 to 4 were examined, and the results are shown in FIG. In FIG. 1, PBI represents the case where a polyvinylbenzimidazole membrane is used as the polymer electrolyte membrane. Here, the cell performance evaluation condition was described. The change in cell potential due to the current density was examined under the non-humidifying condition with the flow rate of hydrogen gas being 100 ml / min and the flow rate of air being 300 ml / min.

  Referring to FIG. 1, the fuel cells of Examples 1 to 4 were found to be equivalent to or better than the fuel cells employing the PBI membrane.

  The ionic conductivity of the polymer electrolyte membranes manufactured according to Examples 1 to 4 was measured and represented in FIG. Here, the ionic conductivity was evaluated by the AC impedance method.

  Referring to FIG. 2, the polymer electrolyte membrane prepared according to Example 1 exhibits the best conductivity, and in Example 3 where both a secondary amine and vinyl pyridine are used, the secondary amine and vinyl pyridine are It was found that the conductivity characteristics are lower than those in the case of using each (Example 2 and Example 4).

(Example 5)
The polymer electrolyte membrane (ion conductivity) was obtained by the same method as in Example 1 except that 10 to 50 parts by mass of vinyl sulfonic acid, which is a monomer containing a sulfonic acid group, was used as the ion conductive polymerizable compound. The coating thickness of the coating film was 5 μm, the polymer electrolyte film thickness was 23 μm), and a fuel cell was manufactured.

  The polymer electrolyte membranes produced according to Example 2, Example 4 and Example 5 were evaluated for their ability to retain phosphoric acid and are shown in Table 2 below. Here, the phosphate retention capacity was evaluated by a method of comparing the weight before impregnation with the change in weight after impregnation.

  From Table 2, the polymer electrolyte membrane obtained using vinylpyridine and amine has a phosphate retention capacity compared to the polymer electrolyte membrane obtained using a compound containing an acidic group such as a sulfonic acid group. I easily found out that it was excellent.

  The conductivity characteristics of the polymer electrolyte membranes manufactured according to Examples 2, 4 and 5 were evaluated and shown in FIG.

  Referring to FIG. 3, a polymer electrolyte membrane manufactured using a monomer containing an amine group has a higher ionic conductivity than a polymer electrolyte membrane manufactured using a compound containing a sulfonic acid group. As a result, it was found that phosphoric acid had a larger amount of impregnation and higher ionic conductivity than the membrane containing amine groups.

  After the polymer electrolyte membrane obtained in Example 3 and Example 5 was swollen (swelled) in phosphoric acid, the state after wiping the surface phosphoric acid was observed using an electron scanning microscope (SEM). 4 and FIG. 5 respectively.

  4 and 5 are SEM magnified photographs of 10,000 times, and it was found that an ion conductive polymer-containing coating film was formed on the outer surface of a single fiber constituting the PTFE matrix. . And if the polymer is coated on the porous polymer matrix and it can be confirmed that each fiber of the polymer is coated, it means that there are pores after coating. The polymer coating is not simply a surface, it is also three-dimensionally coated inside the polymer membrane, the coated ionomer is swelled, and can play the role of securing the proton path during proton transfer While providing a medium, the effect of blocking gas can be confirmed. 4 and FIG. 5 are compared with each other, it can be seen that the polymer electrolyte membrane of Example 3 is far more swollen than that of Example 5. It turns out that it is further superior in liquidity.

  As described above, the polymer electrolyte membrane according to this embodiment is a polymer that has excellent mechanical strength, is not deteriorated by heat even at a temperature of 100 ° C. or higher, and can exhibit excellent ionic conductivity even in a non-humidified state. Yes, suitable for high-temperature fuel cells. The ion conductive polymer coating film formed on the outer surface of the single fiber of the porous polymer matrix constituting the polymer electrolyte membrane and the pores of the polymer matrix has basic functional groups such as pyridine and amine. When formed by using the compound contained, the compatibility with phosphoric acid is further improved after coating, thereby improving the ionic conductivity and cell characteristics at high temperatures. When the polymer matrix constituting the polymer electrolyte membrane is made of a hydrophobic material, when this is applied to DMFC, methanol crossover can be effectively prevented.

  As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

  The polymer electrolyte membrane of the present invention and the fuel cell employing the polymer electrolyte membrane can be effectively applied to, for example, a technical field related to power supply.

It is the graph showing the analysis result of the cell performance of the fuel cell manufactured by Example 1- Example 4 of this invention. It is the graph which measured and represented the ionic conductivity of the polymer electrolyte membrane manufactured by Example 1- Example 4 of this invention. FIG. 6 is a graph showing analysis results for conductivity characteristics in the polymer electrolyte membranes manufactured according to Example 2, Example 4 and Example 5 of the present invention. It is the SEM photograph showing the state after wiping the surface phosphoric acid after swollen the polymer electrolyte membrane obtained by Example 3 of this invention to phosphoric acid. It is the SEM photograph showing the state after swollen the phosphoric acid of the surface, after swollen the polymer electrolyte membrane obtained by Example 5 of this invention to phosphoric acid.

Claims (10)

Using a composition containing an ion conductive polymerizable compound and a crosslinking agent on a porous polymer matrix, and performing vacuum deposition coating of fine particle coating;
To carry out the polymerization reaction of the composition, obtaining a reportage Rimmer electrolyte comprising an ion conducting polymer coating membrane outer surface and formed within the pores of the polymer matrix of a single fiber of the porous polymer matrix A method for producing a polymer electrolyte membrane, comprising: The method according to claim 1 , wherein the fine particle coating is performed by a flash evaporation method. The method for producing a polymer electrolyte membrane according to claim 1 , wherein the composition further includes 20 to 200 parts by mass of a plasticizer based on 100 parts by mass of the ion conductive polymerizable compound. The method for producing a polymer electrolyte membrane according to claim 3 , wherein the plasticizer is at least one selected from the group consisting of poly (ethylene glycol) methyl ether acrylate and polyallyl ether. The method for producing a polymer electrolyte membrane according to claim 1 , wherein the polymerization reaction is performed by irradiating light, using an electron beam, or applying heat. The ion conductive polymerizable compound was selected from vinyl sulfonic acid, styrene sulfonic acid, an acrylic resin having an acidic functional group at the terminal, a C1 to C20 alkylamine, and a vinyl monomer having a basic functional group at the terminal. One or more,
2. The method for producing a polymer electrolyte membrane according to claim 1 , wherein the ion conductive polymerizable compound has a mass average molecular weight of 1000 g / mol or less. The acrylic resin having an acidic functional group at the terminal is a phosphorus monoacrylate or a phosphorus diacrylate,
The alkylamine is acrylic acid 2- (tert-butyl-methylamino) ethyl ester, N-tert-butyldiethanolamine or N- (1-cyanocyclohexyl) -1-N-methylbutyramide;
Vinyl monomer having a basic functional group to the terminal vinyl pyridine, vinyl pyrrolidone, polyethylene imine, and wherein the at least one selected from among 1-vinylimidazole, according to claim 6 A method for producing a polymer electrolyte membrane. The ion conductive polymerizable compound has at least one functional group selected from a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, an imide group, a sulfonimide group, a sulfonamide group, and a hydroxyl group at the terminal, and a head portion. Have an unsaturated bond,
2. The method for producing a polymer electrolyte membrane according to claim 1 , wherein the ion conductive polymerizable compound has a mass average molecular weight of 10,000 g / mole or less. The cross-linking agent is at least one selected from hexyl acrylate, butyl acrylate, trimethylolpropane triacrylate, poly (ethylene glycol) methacrylate, poly (ethylene glycol) dimethacrylate, allyl acrylate, and divinylbenzene. The method for producing a polymer electrolyte membrane according to claim 1 , wherein the method is characterized in that: The method for producing a polymer electrolyte membrane according to claim 1 , wherein the crosslinking agent is 25 to 300 parts by mass based on 100 parts by mass of the ion polymerizable compound.