KR100954699B1 - Photo-crosslinkable aromatic polymer composite membranes for fuel cells and its preparation method - Google Patents

Abstract

The present invention relates to a photocrosslinked aromatic polymer composite membrane for a fuel cell and a method for manufacturing the same, and an object thereof is a specific methylene having a methyl group bonded to an aromatic ring which is not derived from a protonic acid group and does not involve desorption and direct photocrosslinking. SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer membrane for use in a fuel cell, and a method for producing the same, comprising an ion conductive resin using a carbonyl crosslinked structure and a surface-modified microporous olefin base membrane using the same to promote photocrosslinking.

The present invention provides a method for preparing an ion conductive photocrosslinked aromatic polymer composite membrane for fuel cells, comprising: synthesizing a photocrosslinkable ion conductive polymer electrolyte in which a polymer having a repeating unit structure is directly polymerized in a base atmosphere (S1); the photocrosslinkable ion conductive polymer The polymer polymerized in the synthesis step of the electrolyte (S1) is dissolved in a polar solvent, the solution is impregnated into the pores of the microporous hydrocarbon-based base film, laminated between PET films, and then filled with pores of the synthetic polymer electrolyte which is photocrosslinked and heat treated. And a photocrosslinking step (S2); and a method for manufacturing a photocrosslinkable aromatic polymer composite membrane for a fuel cell and a polymer composite membrane manufactured therefrom are characterized by technical features.

Fuel cell, electrolyte membrane, photocrosslinking, low methanol permeability, proton conductivity

Description

Photo-crosslinkable aromatic polymer composite membranes for fuel cells and its preparation method

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocrosslinked aromatic polymer composite membrane for a fuel cell and a method of manufacturing the same. And a method for producing a polymer electrolyte membrane for a fuel cell formed by charging and photografting a microporous polyolefin base membrane to a microporous polyolefin substrate membrane and a polymer electrolyte membrane thereof.

Recently, due to environmental problems, new energy storage or power plants have been strongly requested in society. Fuel cells are also attracting attention as one of them, and they are the most expected generators due to their low pollution and high efficiency. A fuel cell converts chemical energy of a fuel into electrical energy by electrochemically oxidizing a fuel such as hydrogen or methanol using oxygen or air.

Such fuel cells are classified into phosphoric acid type, molten carbonate type, solid oxide type, and polymer electrolyte type according to the type of electrolyte used.

Phosphoric acid fuel cells have already been put to practical use for electric power. However, phosphoric acid fuel cells need to operate at high temperatures (around 200 ° C), which results in a long starting time, difficulty in miniaturizing the system, and inability to obtain large currents due to low ionic conductivity of phosphoric acid. Have

In contrast, the polymer electrolyte fuel cell has a maximum operating temperature of about 80 to 100 ° C. In addition, since the internal resistance in the fuel cell can be reduced by thinning the electrolyte membrane to be used, it can be operated at a high current, thereby miniaturizing it. Due to these advantages, research into polymer electrolyte fuel cells has been actively conducted.

In the polymer electrolyte fuel cell, in addition to the type of using pure hydrogen supplied from a cylinder, a pipe, or the like as a fuel, there is a type of generating and using hydrogen from gasoline or methanol by a reformer. In addition, a direct methanol fuel cell (DMFC: Direct Methanol Fuel Cel1) that directly generates electricity by using an aqueous methanol solution as a fuel has also been developed. Since the DMFC does not require a reformer for generating hydrogen, it is simple and can form a compact system. In particular, the DMFC is drawing attention as a power source for portable equipment.

The polymer electrolyte fuel cell is composed of a polymer electrolyte membrane having ion conductivity and a positive electrode and a negative electrode disposed in contact with both sides thereof. Hydrogen or methanol in the fuel is electrochemically oxidized at the negative electrode to produce protons and electrons. This proton moves to the positive electrode to which oxygen is supplied in the polymer electrolyte membrane. On the other hand, electrons generated at the negative electrode flow to the positive electrode through a load connected to the battery, and protons and electrons react at the positive electrode to generate water. The positive and negative electrodes used in the polymer electrolyte fuel cell are composed of an electrically conductive material, an electrode material such as a catalyst for promoting oxidation of hydrogen and a reduction of oxygen, and a binder for fixing the electrode. do

Generally, highly sulfonated polymers are required to obtain ion conductive polymer electrolyte membranes with high photoconductivity, but such polymers have a problem in that they are easily dissolved in water due to increased hydrophilicity (Japanese Patent Application Laid-Open No. 10-45913). Etc). Since the fuel cell is a by-product of water by the reaction of fuel and oxygen, there is a problem that the water-soluble resin cannot be used as a polymer electrolyte membrane for fuel cells.

In addition, even if the water is not water-soluble, high hygroscopic properties include problems such as swelling of the membrane, a decrease in strength, and methanol crossover through absorbed water.

On the other hand, as a method of reducing water solubility and suppressing elution of resins without introducing a component having no water solubility, a crosslinked structure by covalent bonds has attracted attention. (8 in Korean Patent No. 10-0660433) See page 9)

As a method for solving the conventional problems as described above, in WO 2003/033566, a crosslinking mechanism which can be crosslinked during or after film formation, is not derived from a protonic acid group, and does not involve desorption components. Although the photocrosslinked aromatic polymer electrolyte membrane was prepared by using an alkyl group having 1 to 10 carbon atoms and a carbonyl group directly bonded to the compound, it was noted that it was possible to prepare a membrane in which at least 10% of the resin was not dissolved in methanol. In the chemical structure, it was confirmed that the crosslinking reaction was not sufficiently expressed under the same photocrosslinking conditions.

An object of the present invention for solving the above problems is an ion conductive resin using a specific methylene and carbonyl crosslinked structure in which a methyl group is bonded to an aromatic ring which is not derived from a protonic acid group and does not involve desorption and directly expresses photocrosslinking. And an ion-conducting polymer membrane for use in a fuel cell, and a method for producing the same, which use the surface-modified microporous olefin base membrane which promotes photocrosslinking using the same.

In the present invention to achieve the object as described above and to perform the problem for eliminating the conventional drawbacks in the method for producing ion conductive photocrosslinked aromatic polymer composite membrane for fuel cells,

Synthesis step (S1) of the photo-crosslinkable ion conductive polymer electrolyte for directly polymerizing a polymer having a repeating unit structure represented by the general formula 1 in a base atmosphere;

The polymer polymerized in the synthesis step (S1) of the photocrosslinkable ion conductive polymer electrolyte is dissolved in a polar solvent, the solution is impregnated in the pores of the microporous hydrocarbon-based base film, laminated between PET films, and then photocrosslinked and heat treated. It is achieved by providing a method for producing an ion conductive photocrosslinked aromatic polymer composite membrane for a fuel cell, characterized in that consisting of; pore filling and photocrosslinking step (S2) of the synthetic polymer electrolyte.

<Formula 1>

In the above, x and y are greater than 0, x + y = 1, n = 1 or more integer

In the general formula, x = 0.5 to 0.8, it is characterized in that it is synthesized in a structure of y = 0.5 to 0.2.

In the pore filling and photocrosslinking step (S2) of the synthetic polymer electrolyte, the microporous polyolefin substrate membrane has a pore volume of 30 to 70%, a pore size of 0.05 to 0.1 micrometers, and a thickness of 10 to 50 micrometers. It is characterized by using a phosphorus polyolefin membrane.

The polyolefin microporous substrate membrane is immersed in a solution in which a concentration of 98% or more sulfuric acid and a concentration of 96% or more sulfuric acid chloride are mixed at a weight ratio of 1: 1 to 3: 1, followed by reaction with a sodium hydroxide solution having a normal concentration of 1-3. It is characterized in that it is prepared through a step of washing the substrate film by sulfonation and hydrophilization for at least one day.

In the pore filling and photocrosslinking step (S2) of the synthetic polymer electrolyte, the polymer material having a repeating unit structure represented by Formula 1 prepared in the synthesis step (S1) of the photocrosslinkable ion conductive polymer electrolyte It is characterized in that the solution is prepared by dissolving to 30 to 50% by weight in one of the polar solvent of the pore filling and photocrosslinking step (S2).

The polyolefin microporous substrate membrane was immersed in the solution prepared above, laminated between two transparent PET films, and then irradiated with ultraviolet energy of 15,000 to 30,000 mJ / cm ² under nitrogen atmosphere to photocrosslink in a sulfonated hydrophilized substrate. It is characterized by forming a film.

The prepared crosslinked film is heat-treated at 110 to 120 ° C. for at least 1 hour in a state where the transparent PET film is not removed, further comprising the step of inhibiting the swelling degree of the polymer film by increasing solvent removal and crosslinking density.

The polar solvent is one polar solvent selected from dimethyl acetamide (DMAc), nitromethylpyrrolidone (NMP), dimethyl sulfoxide (DMSo), dimethyl fluoride (DMF).

The present invention is an ion conductive optical crosslinked aromatic polymer composite membrane for fuel cells,

It is achieved by providing an ion conductive photocrosslinkable aromatic polymer composite membrane for a fuel cell, which is prepared by the above method and has a polymer composite membrane having a proton conductivity of 0.03 S / cm or more and methanol permeability of 0.28 kg / m ² · h or less.

Ionic conductive resin using a specific methylene and carbonyl crosslinked structure in which a methyl group is bonded to an aromatic ring that is not derived from a protonic acid group and does not involve detachment but directly expresses photocrosslinking, and a surface-modified surface that promotes photocrosslinking using the same The photocrosslinked polymer electrolyte composite membrane of the present invention prepared using a microporous olefin substrate membrane has a proton conductivity that is not yet at the level of commercial membrane, but has excellent tensile strength and methanol permeability compared to the commercial membrane. If it is stable to 1/2 level to improve the proton conductivity, it can replace the commercial membrane as a low-cost eco-friendly hydrocarbon fuel cell membrane.

In addition, when the amount of UV irradiation is 15,000 mJ / cm ² or more, spontaneous crosslinking reaction proceeds without the photoinitiator, and most of the complete crosslinking is a useful invention with the advantage that it is not dissolved in an organic solvent is an invention that is expected to be used industrially greatly.

Hereinafter, the configuration and the operation of the embodiment of the present invention will be described in detail with reference to the accompanying drawings.

The present invention relates to a crosslinked ion conductive polymer membrane by photocrosslinking polymerization of a specific methylene having a methyl group bonded to an aromatic ring with a carbonyl crosslinked structure or a surface-modified microporous polyolefin substrate membrane and a method for producing the same. The photocrosslinked polymer electrolyte according to the present invention is characterized by having a structure such as the following general formula in which photocrosslinking is directly expressed without detachment component by spontaneous initiation reaction in a polymer structure that does not use a photoinitiator.

In the polymer of the above structure produced in the present invention, x + y = 1, n = 1 or more integer. If x is not present, proton conductivity cannot be obtained, and without y, spontaneous photocrosslinking cannot be achieved. Preferably it should be synthesized in a structure of x = 0.5 to 0.8, y = 0.5 to 0.2. The reason for this limitation is that if x is less than 0.5 (y is greater than 0.5), there is less sulfonic acid and thus no specific proton conductivity can be obtained. If it is greater than 0.8 (y is less than 0.2), the crosslinking density is small so that it is easy to be used in an organic solvent. It is because it melt | dissolves and a film property falls. In spontaneous photocrosslinking reaction without photoinitiator, radicals are generated as ketones in the polymer structure excite electrons by ultraviolet irradiation, and the generated radicals attack methylbenzene, resulting in a chain radical reaction.

The polymer of the structure prepared in the present invention is directly polymerized in a base atmosphere, the polymerized polymer is dimethyl acetamide (DMAc), nitromethylpyrrolidone (NMP), dimethyl sulfoxide (DMSo) dimethyl fluoride (DMF Soluble in a polar solvent such as). Thereafter, the dissolved solution is impregnated in the pores of the microporous hydrocarbon-based base film, laminated between PET films, and then crosslinked and heat treated to prepare a composite film. The polar solvent used in the present invention is not limited to the four solvents mentioned above, and is based on the high solubility of the synthesized polymer, and if the solubility is sufficient, both polar solvents may be used.

The microporous polyolefin substrate membrane according to the present invention has a pore volume of 30 to 70%, (proton conductivity is very low to be used as a fuel cell membrane when the pore volume is less than 30%, and the mechanical strength of the composite membrane is lowered when it is greater than 70%. More preferably, it is 35 to 50%, and the pore size is 0.05 to 0.1 micrometers (the pore size is less than 0.05, it is difficult to fill the electrolyte. If the pore size is larger than 0.1, the swelling inhibiting effect of the composite membrane is expressed.) More preferably, 0.07 to 0.1 micrometers, polyolefin membranes having a thickness of 10 to 50 micrometers, and more preferably 15 to 30 micrometers. It is possible to improve fuel cell performance by minimizing the thickness of the membrane while increasing the above.

The polyolefin microporous substrate membrane is a 1: 1 to 3: 1 weight ratio of sulfuric acid with a concentration of 98% or more and sulfuric acid with a concentration of 96% or more. (The reason for the numerical limitation is that the sulfonic hydrophilization of the substrate is performed by sulfuric acid chloride. It is used as a solvent, and the ratio of 1: 1 to 3: 1 is an optimal condition for increasing the sulfate ion mobility of sulfuric acid chloride in the solvent and at the same time to accelerate the sulfonation of the substrate membrane.) 30-60 ° C. (The reason for such numerical limitation is that the rate of sulfone hydrophilization is significantly slower at room temperature and the base film is damaged at a temperature higher than 60 degrees, so that the desired sulfone hydrophilization cannot be obtained.), After reacting at 45 to 50 ℃ for 2 to 5 hours, preferably 3 to 4 hours, 1 to 3 normal concentration (the reason for such numerical limitation is that when the concentration is greater than 3, there is a problem of promoting hydrolysis of the membrane, 1 If it is low, there is a problem that it is not easy to remove the remaining chloride, so that more than 1 day (if less than 1 day, sufficient sulfone hydrophilization can not be achieved, longer time than that Since the sulfonation is progressed, there is no significant meaning of sulfonated hydrophilicity, and if it is too long, it may cause problems of damage caused by sulfuric acid solvent for a long time.) Cleaning and sulfonated hydrophilic substrate to increase the filling rate of the polymer electrolyte and photocrosslinking reaction. To promote.

The polymer electrolyte prepared above is 30 to 50% by weight in one of polar solvents such as dimethylacetamide (DMAc), nitromethylpyrrolidone (NMP), dimethyl sulfoxide (DMSo) and dimethyl fluoride (DMF), ( The reason for this limitation is that if the amount is less than 30%, the electrolyte is not sufficiently filled in the base film, and if it is more than 50%, the viscosity of the electrolyte solution is so high that it is difficult to fill the electrolyte in the base film.) After dissolving to 40 to 45% by weight to prepare a solution, the sulfonated hydrophilized substrate was prepared for 5 to 60 seconds (the reason for this limitation is less than 5 seconds. Is not significant since the pore filling is completed), preferably immersed for 10 to 30 seconds, and 30 to 100 micrometers. In heat If it is larger than 100, the composite film is difficult to adhere completely between the PET films, and thus the reactivity is poor.), 15,000 under a nitrogen atmosphere after lamination between two transparent PET films, preferably 30 to 50 micrometers thick. Ultraviolet energy of ˜30,000 mJ / cm ² (the reason for the numerical limitation is that the crosslinking is hardly achieved at a dose of less than 15000, and a dose higher than 30000 is not significant since the crosslinking reaction is already completed.) The photocrosslinking reaction proceeds in the sulfonated hydrophilic substrate, the polymer density increases due to the crosslinking, and the membrane permeation phenomenon of methanol can be suppressed. Therefore, it is used in the polymer electrolyte membrane fuel cell including the methanol fuel cell directly. Can improve electrical performance.

In addition, the prepared optical cross-linked polymer electrolyte composite membrane is 110 ~ 120 ℃ without removing the transparent PET film (the reason for the numerical limitation is that the film is thermally damaged if it is 120 ℃ or more, if the lower than 110 ℃ remaining organic solvent In this case, the swelling problem of the fluorine-based commercial membrane can be solved by suppressing the swelling degree of the polymer membrane to the maximum by removing the solvent and increasing the crosslinking density by heat treatment for 1 hour or more.

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited at all by this. Various tests and performance evaluations of the ion conductive polymer membranes prepared in Examples and Comparative Examples of the present invention were carried out in the following manner.

1. Tensile strength

The tensile force (kpsi) of the electrolyte membrane was measured according to the method described in ASTM 882.

2.proton conductivity

The membrane prepared in Examples and Comparative Examples was immersed in distilled water at 25 ° C. for 1 hour, and then placed between two glass substrates on which a rectangular platinum electrode was fixed without removing water from the membrane surface to fix the glass substrate. Hz to 4 MHz AC impedance measurements were performed to measure the proton conductivity of the membrane.

3. Methanol transmittance

An electrolyte membrane sample was mounted in the methanol permeability measuring apparatus shown in FIG. 1, and then 10 wt% methanol solution was placed in a container on the left side of the membrane, and distilled water was placed on the right side of the membrane. Methanol is the membrane through the sample, so go to distilled direction with the lapse of time, has elapsed, a distilled water-side solution to gas chromatography measurement through membrane methanol permeability by some collected 2 hours at room temperature conditions (kg / m ² · h) Was calculated.

(Example)

1) Synthesis step of photocrosslinkable ion conductive polymer electrolyte

6.8775 g (0.014 mol) of sulfonated dichlorodiphenylsulfone sodium salt, 1.5067 g (0.006 mol) of dichlorobenzophenone, 5.1268 g (0.02 mol) of 3, 3 ', 5, 5'-tetramethyl-4, 4'-methylenediphenol, 20 ml of NMP After complete dissolution in a 200 ml volume three-necked flask equipped with Dean-stark trap for nitrogen filling and solvent reflux with 3.455 g (0.025 mol) of anhydrous potassium carbonate, fully dispersed and further added 20 ml of toluene It was stirred at room temperature for 1 hour.

Then, while raising the temperature to 145 ℃ under a nitrogen atmosphere, the water produced by the polymerization reaction was removed using the reflux of toluene vaporized together at the azeotropic point.

After maintaining the reaction for 5 hours at the same temperature, the reaction was polymerized for 20 hours by increasing the temperature to 185 ℃.

After the reaction was completed, the polymer solution was cooled to room temperature, and then 40 ml of NMP was added dropwise to dilute the polymer solution. A membrane filter was used to remove unreacted potassium carbonate and potassium chloride by-products, and the polymer solution was removed in an appropriate amount. Poured into propyl alcohol to remove unreacted monomer and precipitate the synthetic polymer electrolyte. The precipitated polymer electrolyte was vacuum dried at 120 ° C. for 12 hours, and then dissolved again in NMP at a concentration of 40 wt% to fill the electrolyte.

2) Hydrophilic treatment step based on microporous polyolefin

After cutting the microporous polyethylene substrate (Asahi Kasei Chemicals, Japan) having a pore volume of 30%, an average pore size of 0.1 micrometer, and a thickness of 30 micrometers to an appropriate size, sulfuric acid having a concentration of 98% or more and sulfuric acid chloride of 96% or more The substrate was immersed in a mixed solution at a weight ratio of 1 to 1, and reacted at 40 ° C for 3 hours to hydrophilize the substrate. In order to remove the chlorides remaining on the hydrophilized substrate, the solution was washed with a sodium hydroxide solution of 2 normal concentrations for at least 1 day, and then dried in an oven at 70 ° C. for 2 hours or more to prepare a sulfonated hydrophilic substrate.

3) Pore filling and photocrosslinking step of synthetic polymer electrolyte

The substrate prepared in the hydrophilic treatment step of the microporous polyolefin substrate of 2) was immersed in the polymer electrolyte solution prepared in the synthesis step of the photocrosslinkable ion conductive polymer electrolyte of 1) for 30 seconds to completely fill the polymer electrolyte in the micropores. It was. Substrate filled with a polymer electrolyte was placed between two PET films 50 micrometers thick, and the PET film was completely adhered to remove the excess polymer electrolyte solution and placed in a 340 nm wavelength curing UV (UV) device. The photocrosslinking was carried out at 30 minutes at 1 hour at 500 mJ / cm ² dose without adding photoinitiator. After the photocrosslinking reaction was completed, the film was heat-treated at 110 ° C. for 1 hour without removing the PET film, thereby slowly removing the remaining solvent and increasing the crosslinking density. After the PET film was removed, the polymer on the surface was removed with water, and the polymer electrolyte was completely replaced with acid by putting it in hydrochloric acid at 2 normal concentration. Tensile strength, proton conductivity, and methanol permeability of the polymer electrolyte composite membrane substituted with acid were measured, and the results are shown in Table 1 below. In addition, the weight after drying of the polymer electrolyte composite membrane prepared by photocrosslinking in order to check the cross-linking according to the light irradiation time, and put in a dimethyl acetate solvent for 1 hour at room temperature, followed by 100% methanol solution for at least 1 day After washing and drying with water, the weight was measured, and the results of comparing the remaining polymer electrolyte are shown in FIG. 1.

Comparative example)

Tensile strength, proton conductivity, and methanol permeability of a commercial Nafion 117 membrane (Dupont, USA), which are commercially available ion exchange membranes, are shown in Table 1 and compared with Examples.

TABLE 1

The photocrosslinked polymer electrolyte composite membrane of Examples prepared in the present invention from Table 1 has a proton conductivity that is not yet at the level of a commercial membrane, but has excellent tensile strength and a methanol permeability of the membrane of the Comparative Example, compared to the membrane of the Comparative Example. If it is stable to 1/2 level and improves the proton conductivity further, it can replace the commercial membrane of the comparative example as a low cost environmentally friendly hydrocarbon fuel cell membrane.

In addition, it can be seen from FIG. 2 that the photocrosslinked polymer electrolyte composite membrane prepared according to the present invention is spontaneous crosslinking reaction without photoinitiator when the UV irradiation amount is 15,000 mJ / cm ² or more, so that most of the crosslinking is completely dissolved and not dissolved in an organic solvent. have.

The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

1 is a schematic diagram of a device for measuring the methanol permeability of the polymer electrolyte membrane prepared in Examples and Comparative Examples,

Figure 2 is a result showing the change amount of the residual polymer electrolyte after washing the organic solvent in order to confirm the crosslinking density according to the light irradiation time of the optical crosslinked polymer electrolyte composite membrane prepared in Example.

Claims (9)

In the method for producing an ion conductive photocrosslinked aromatic polymer composite membrane for a fuel cell, Synthesis step (S1) of the photo-crosslinkable ion conductive polymer electrolyte for directly polymerizing a polymer having a repeating unit structure represented by the general formula 1 in a base atmosphere; The polymer polymerized in the synthesis step (S1) of the photocrosslinkable ion conductive polymer electrolyte is dissolved in a polar solvent, the solution is impregnated in the pores of the microporous hydrocarbon-based base film, laminated between PET films, and then photocrosslinked and heat treated. Pore filling and photo-crosslinking step of the synthetic polymer electrolyte (S2); The microporous polyolefin substrate membrane of the pore filling and photocrosslinking step (S2) of the synthetic polymer electrolyte has a pore volume of 30 to 70%, a pore size of 0.05 to 0.1 micrometers, and a thickness of 10 to 50 micrometers. A polyolefin membrane is used, and the polyolefin microporous substrate membrane is immersed in a solution mixed with a sulfuric acid concentration of 98% or more and sulfuric acid chloride of 96% or more in a ratio of 1: 1 to 3: 1 by weight, and then reacted with a concentration of 1 to 3 normal. A method for producing a photocrosslinked aromatic polymer composite membrane for a fuel cell, which comprises manufacturing the substrate membrane by washing with a sodium hydroxide solution for at least one day and then sulfonating the substrate membrane. <Formula 1>

In the above, x and y are greater than 0, x + y = 1, n = 1 or more integer The method of claim 1, In the general formula x = 0.5 to 0.8, y = 0.5 to 0.2, characterized in that the synthesis method for producing a light-crosslinked aromatic polymer composite membrane for a fuel cell. delete delete The method of claim 1, In the pore filling and photocrosslinking step (S2) of the synthetic polymer electrolyte, the polymer material having a repeating unit structure represented by the general formula (1) prepared in the synthesis step (S1) of the photocrosslinkable ion conductive polymer electrolyte is a pore of the synthetic polymer electrolyte. Method for producing a light-crosslinked aromatic polymer composite membrane for a fuel cell, characterized in that the solution is prepared by dissolving so that 30 to 50% by weight in one of the polar solvent of the filling and photocrosslinking step (S2). The method of claim 5, The polyolefin microporous substrate membrane was immersed in the prepared solution, laminated between two transparent PET films, and then irradiated with ultraviolet energy of 15,000 to 30,000 mJ / cm ² under a nitrogen atmosphere to photocrosslink in a sulfonated hydrophilized substrate to form a membrane. A method for producing a photocrosslinked aromatic polymer composite membrane for a fuel cell, characterized in that it is formed. The method of claim 6, The prepared cross-linked film is heat-treated at 110 to 120 ° C. for at least 1 hour in a state where the transparent PET film is not removed, further comprising the step of inhibiting the swelling degree of the polymer film by increasing solvent removal and cross-linking density. Method for producing a crosslinked aromatic polymer composite membrane. The method of claim 1, The polar solvent is a photocrosslinked aromatic polymer for a fuel cell, characterized in that one polar solvent selected from dimethyl acetamide (DMAc), nitromethylpyrrolidone (NMP), dimethyl sulfoxide (DMSo), dimethyl fluoride (DMF) Composite membrane manufacturing method. In the ion conductive optical crosslinked aromatic polymer composite membrane for fuel cell, Prepared by the method according to any one of claims 1, 2, 5, 6, 7, 8, proton conductivity is 0.03 S / cm or more, methanol permeability 0.28 kg / A photocrosslinkable aromatic polymer composite membrane for a fuel cell, characterized by a polymer composite membrane of m ² · h or less.

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