KR20010061632A - Fabrication method of the composite polymer membrane and composite polymer membrane/electrode assembly for polymer electrolyte membrane fuel cell - Google Patents

Abstract

PURPOSE: A method for preparing a composite polymer membrane of polymer electrolyte membrane fuel cell(PEMFC) is provided, which lowers a price of the polymer membrane, produces the electrolytic polymer membrane having a relatively thin thickness and reduces expansion and contraction of the polymer membrane. And a method for preparing a composite polymer membrane/electrode assembly by using the same is provided. CONSTITUTION: The method for preparing a composite polymer membrane comprises steps of: (i) hot pressing or rolling a perfluorosulfonylfluoride/TFE copolymer resin at 200-250 deg.C to obtain a pre-formed precursor sheet; (ii) after inserting a porous membrane in the center of the pre-formed precursor sheet, hot pressing or rolling it to obtain a composite sheet of the pre-formed precursor and the porous membrane; (iii) treating the composite sheet with an aqueous solution of sodium hydroxide in a 5-30 weight ratio to convert the composite pre-formed sheet consisting of the composite perfluorosulfonylfluoride/TFE copolymer resin into a Na+ formed composite perfluorosulfonate polymer membrane; and (iv) hydrating the Na+ formed composite perfluorosulfonate polymer membrane to convert it into a H+ formed composite perfluorosulfonate polymer membrane. The composite polymer membrane/electrode assembly is prepared by the steps of: (i) hot pressing or rolling a perfluorosulfonylfluoride/TFE copolymer resin at 200-250 deg.C to obtain a pre-formed precursor sheet; (ii) after inserting a porous membrane in the center of the pre-formed precursor sheet, hot pressing or rolling it to obtain a composite sheet of the pre-formed precursor and the porous membrane; (iii) treating the composite sheet with an aqueous solution of sodium hydroxide in a 5-30 weight ratio to convert the composite pre-formed sheet consisting of the composite perfluorosulfonylfluoride/TFE copolymer resin into a Na+ formed composite perfluorosulfonate polymer membrane; (iv) coating the Na+ formed composite perfluorosulfonate polymer membrane with a platinum catalyst ink; and (v) hot pressing the catalyst ink coated composite polymer membrane at 120-200 deg.C to produce a composite polymer membrane/electrode assembly.

Description

Manufacturing method of composite polymer membrane and composite polymer membrane / electrode assembly for polymer fuel cell {FABRICATION METHOD OF THE COMPOSITE POLYMER MEMBRANE AND COMPOSITE POLYMER MEMBRANE / ELECTRODE ASSEMBLY FOR POLYMER ELECTROLYTE MEMBRANE FUEL CELL}

The present invention relates to a method for producing a composite polymer membrane and a composite polymer membrane / electrode assembly (MEA) for a polymer electrolyte fuel cell (PEMFC).

Generally, fuel cell is a high-efficiency clean power generation technology that directly converts hydrogen and oxygen contained in hydrocarbon fuel such as methanol and natural gas into electric energy by electrochemical reaction. Since it was developed for power supply for spacecraft or military, researches on using it as a general power source have been actively conducted, and research and development for its practical use are currently being actively conducted in advanced countries such as the United States, Japan and Europe.

Fuel cells are classified into alkali type, phosphoric acid type, molten carbonate, solid oxide, and polymer fuel cells according to the type of electrolyte used. Among the various types of fuel cells, the polymer electrolyte membrane fuel cell uses a polymer as an electrolyte, so there is no risk of corrosion or evaporation by the electrolyte, and a high current density per unit area can be obtained. Compared with fuel cells, its output characteristics are much higher and its operating temperature is so low that it can be used as a portable power source for automobiles, small power sources such as on-site and electronic devices for homes and public buildings. In Europe, Japan and Europe, the development of this is being actively promoted.

The fuel cell stack body, which forms the center of such a polymer fuel cell power generation system, has a fuel electrode and an air electrode on both sides of a solid electrolyte made of a proton-exchange membrane. It consists of a single cell constructed by attaching an air electrode by hot pressing, and stacks these unit cells in multiple layers to achieve fuel cell power generation from several W to several hundred kW. It constitutes a fuel cell power plant system.

Meanwhile, in the power generation system of the polymer fuel cell, the performance of the membrane / electrode assembly (MEA) has a great influence on the power generation characteristics. The polymer membrane / electrode assembly is composed of a solid polymer electrolyte membrane and a carbon supported catalyst electrode layer. The polymer electrolyte membrane is Nafion (trade name manufactured by DuPont) and Premion. Perfluorosulfonate ionomer membranes such as (Flemion, trade name manufactured by Asahi Glass), Asifrex (Asiplex, trade name manufactured by Asahi Chemical), and Dow XUS (Dow XUS, trade name manufactured by Dow Chemical) Perfluorosulfonate ionomer membrane is widely used, and the carbon-supported catalyst electrode layer supports fine catalyst particles such as platinum (Pt) or ruthenium (Ru) on an electrode support such as porous carbon paper or carbon cloth. The carbon powder is combined with a waterproof binder and used.

Since the polymer electrolyte membrane used at present is quite expensive, the polymer electrolyte membrane is a major problem in commercializing the polymer fuel cell as a power source for power generation.

As a way to solve this problem, if a porous membrane made of relatively inexpensive PTFE etc. is combined with the existing electrolyte membrane, the use of expensive existing electrolyte membrane can be reduced, and this method is also used. It is known that it is possible to produce an electrolyte membrane having a very thin thickness.

In addition, stable mechanical properties of the polymer membrane can be obtained by reducing the large expansion and contraction of the polymer membrane generated by moisture in the existing electrolyte membrane using the composite electrolyte membrane.

In the direct methanol fuel cell (DMFC) using the conventional polymer electrolyte membrane, there is a disadvantage in that the performance of the fuel cell is significantly lowered by the methanol crossover from the anode to the cathode through the polymer electrolyte membrane. The hydrophobic porous membrane can be put into the polymer electrolyte membrane to make a composite membrane to solve this disadvantage. Accordingly, in recent years, a technique for producing a composite polymer membrane for a polymer fuel cell has been known.

Recently, Nafion solutions in porous support materials such as PTFE (polytetrafluoroethylene), Celgard, polycarbonate, and PVDF (polyvinylidene fluoride) Conventional methods for preparing composite membranes by impregnation of Nafion solution are known. (Reference: J.-S. Jiang, DB Greenberg, and JR Fried, Preparation of a Nafion composite membrane using a porous teflon support, J. Membrane Science , Vol. 132, pp. 273-276, 1997, and KM Nouel and PS Fedkiw, Nafion-based composite polymer electrolyte membrane, Electrochimica Acta , Vol. 43, No. 16- 17, pp. 2381-2387, 1998)

However, according to the conventional method, a composite membrane prepared by casting a Nafion solution at room temperature is brittle, brittle, easily cracked, and easily soluble in water or polar organic solvents. There is this.

In order to improve the properties of the casting film, a method of adding a high-boiling solvent to the Nafion solution or adopting a separate annealing step of 200-250 ° C. has been attempted. The composite membranes have higher gas permeability than conventional Nafion membranes, and there are many reactant crossovers of reactant fuels and oxidants, and thus they are intermixed in fuel cells.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems raised in the method of manufacturing a composite polymer membrane of a conventional polymer fuel cell, and to obtain a perfluorosulfonyl fluoride / when hot pressing or rolling for producing the composite polymer membrane. A composite polymer membrane of a polymer fuel cell in which a polymer polymer resin is adhered to a porous support membrane by melting of perfluorosulfonylfluoride / TFE copolymer resin and embedded into the porous support membrane, thereby causing adhesion and complexation of the polymer membrane and the porous support membrane. An object of the present invention is to provide a method for producing a polymer membrane / electrode assembly.

1 is a manufacturing process of the composite polymer film and the composite polymer film / electrode assembly according to the present invention.

Figure 2 is a cross-sectional view of the composite membrane / electrode assembly produced by the manufacturing process according to the present invention.

3 is a scanning electron micrograph of the cross section of a single polymer membrane / electrode assembly of the present invention.

Figure 4 is a scanning electron micrograph of the cross-section of the composite polymer film / electrode assembly of the present invention.

Figure 5 is a graph comparing the change between the current density versus the cell voltage for the unit cell of the polymer membrane / electrode assembly prepared with a single polymer membrane and a composite polymer membrane, respectively.

Figure 6 is a graph comparing the change between the current density versus the cell voltage for the unit cell of the polymer membrane / electrode assembly prepared of the composite polymer membrane and commercial Nafion polymer membrane of the present invention.

((Description of the code for the main part of the drawing))

1. anode catalyst layer 2. cathode catalyst layer

3. Ion exchange polymer membrane 4. Porous PTFE membrane

In the method of manufacturing a composite polymer film according to the present invention for achieving the above object, a preform precursor sheet (pre-formedprecursor) of a predetermined form by hot pressing or rolling using a polymer resin (prepolymer) as a precursor (precursor) sheet 2), and then the porous support membrane is placed in the sheet, and the porous support membrane is embedded at the contact surface by melting the preform sheet by hot pressing or rolling, and then caustic soda (NaOH) solution. The composite polymer membrane is obtained by performing hydration treatment in the polymer membrane to ionize the polymer membrane.

1 is a process chart of the composite polymer film production method of the present invention based on the composite polymer film production process of the present invention in detail as follows.

First, in the present invention, perfluorosulfonyl fluoride / TF copolymer resin (perfluorosulfonylfluoride / TFE copolymer resin) is used as a raw material for forming a polymer film.

On the other hand, perfluorosulfonate ionomer membranes are melt-processable due to side chain entanglement and ionic interactions between functional groups. On the other hand, perfluorosulfonylfluoride / TFE copolymer resins as precursors to the perfluorosulfonate ionomer membranes are readily sheetable as they have melt moldability. ) And tube (tube), etc. can be formed into various forms.

The perfluorosulfonyl fluoride / TF forms the pre-formed sheet by hot pressing or rolling the copolymer resin at a temperature of 200-250 ° C.

Next, the porous PTFE membrane is placed in the middle of the two sheets, and then hot pressed or rolled to a temperature of 200-250 ° C.

The hot pressing or rolling process causes the preform precursor membrane to melt on its surface, and as a result, the molten preform precursor membrane is embedded into the pores of the porous PTFE membrane, thereby forming two preform precursor membranes and the porous PTFE membrane. Will create a fully bonded complex.

The porous PTFE membrane is chemically stable against almost all solvents or chemicals such as methanol, ethanol, hydrochloric acid, or sulfuric acid, has no thermal transformation even up to 260 ° C, and is hydrophobic so that it does not get wet with water-containing materials. Have

Since the composite polymer membrane obtained through the hot pressing or rolling process is not in an ionized form, a hydration treatment for converting the composite polymer membrane into an ionized form is performed as a subsequent step. This hydration treatment is performed by immersing the composite polymer membrane in a caustic soda (NaOH) solution or sulfuric acid (H ₂ SO ₄ ) solution so that the perfluorosulfonyl fluoride membrane is a Na ⁺ or H ⁺ type perfluorosulfonate membrane ( By converting into a perfluorosulfonate membrane), the composite polymer membrane of the present invention is obtained.

The composite polymer membrane of the fuel cell prepared by the method of the present invention is embedded in the PTFE membrane voids by melting of the preform sheet during hot pressing or rolling process between the preform sheet and the PTFE membrane, and the interface between them is caused to melt. This eliminates the risk of delamination between the two different materials, and is characterized by a very low gas permeability of the resulting composite membrane.

Embodiments of the present invention are as follows.

First, perfluorosulfonyl fluoride / TF copolymer resin (perfluorosulfonylfluoride / TFE copolymer resin) was prepared. Perfluorosulfonyl fluoride / TF copolymer copolymer resin is an ellipsoidal powder or size of about 3.6 (L) x 2.4 (W) x 1.5 (T) (mm) consisting of spherical particles having a particle size distribution of 20-200 μm. It is made of particles.

Differential thermal analysis (DTA) and thermogravimetric analysis (TG) of the precursor were heated to 700 ° C. at a rate of 10 ° C./min in air to determine the molding conditions of the preform precursor sheet. Was performed.

Exothermic reactions and weight reductions start at about 380 ° C. and end at about 500 ° C. The weight loss curve showed that the precursor completely pyrolyzed at about 500 ° C. Therefore, the precursor must be preformed in the temperature range below 380 ° C.

Preform precursor sheets were fabricated using precursors at various temperature ranges between 200 ° C. at which precursor melting started and 380 ° C. at which pyrolysis began. The preform precursor sheet was produced by a hot pressing or rolling process at a temperature of 200 ° C to 250 ° C to form a uniform sheet without pores.

In order to prepare a composite polymer membrane, various porous PTFE membranes having a thickness ranging from 15 to 100 μm were used. These porous PTFE membranes had a pore size of 1-5 μm and a porosity of 80-90%.

In the embodiment of the present invention, a pore size of 1 to 3 µm and a thickness of 10 to 15 µm were mainly used. The surface of this membrane showed the structure of a typical porous PTFE.

The composite polymer membrane made of a porous PTFE membrane and a preform polymer sheet was prepared by hot pressing or rolling process using the melting characteristics of the copolymer resin. The surface of the preform precursor film is melted at 200 to 250 ° C. so that the molten precursor is embedded into the porous PTFE voids.

On the other hand, since the composite polymer precursor membrane obtained through the hot pressing or rolling process is not ionized, it must be converted into an acid type ion-exchange membrane by hydrolysis. To this end, the precursor film was kept in a 5-30% caustic soda / methanol (2: 1 volume ratio) solution at 90 ° C. for 7 hours, and then taken out and washed several times with de-ionized water.

As a result of this hydration treatment, the composite perfluorosulfonyl fluoride membrane was converted into a composite perfluorosulfonate membrane in the form of Na ⁺ . At this time, by adding methanol (volume ratio 2: 1) in a 5-30% caustic soda solution (NaOH), wetting and swelling properties of the polymer membrane may be enhanced.

Next, platinum coated carbon (20% Pt / C) was mixed with Nafion solution, glycerol, and tetrabutyl ammonium hydroxide (TBAOH) to prepare a catalyst ink. At this time, the viscosity of the catalyst ink and the dispersion degree of the carbon coated with platinum are controlled by adding glycerine and Nafion solution.

Printing or spray coating of catalyst ink on film to a certain size using screen printing technology and spray technology or doctor blade technology for mass production It was.

The printed or spray coated catalyst ink was dried in a vacuum dryer at 100-150 ° C. for 5 hours. The dried pattern was hot pressed at 195 ° C. by hot pressing to be pressed onto the composite membrane to prepare a composite electrolyte membrane / electrode assembly (MEA).

The Na ⁺ composite polymer membrane / electrode assembly prepared through the above process was converted to H ⁺ type ion exchange membrane by soaking for 2-3 hours in 0.1-1M sulfuric acid (H ₂ SO ₄ ) solution at 90 ° C. The conjugate thus converted was taken out and washed with de-ionized water several times to prepare a composite polymer membrane / electrode assembly (MEA) according to the present invention.

On the other hand, in order to prepare a composite polymer membrane / electrode assembly by compressing the H + type composite polymer membrane with an electrode supporting electrode, the Na ⁺ type composite perfluorosulfonate polymer membrane was additionally added in an aqueous solution of 0.1-1 M sulfuric acid. By hydration, a composite perfluorosulfonate polymer membrane in H ⁺ form was prepared.

A process of compressing the electrode support coated with the catalyst slurry on the H ⁺ type composite perfluorosulfonate polymer membrane was carried out.

First, the catalyst slurry made of platinum (Pt) coated carbon powder (Pt / C), Teflon (PTFE) solution, crosslinking agent and peptizing agent is uniformly screen printed and spray coated on waterproof carbon paper or carbon cloth as electrode support. Or by performing a doctor braid coating process, drying the coated electrode in an inert gas atmosphere at 200 to 250 ° C., and sintering the dried electrode in an inert gas atmosphere at 300 to 370 ° C. for 10 to 50 minutes. A support coated electrode was prepared. The electrode support coated electrode was pressed to the H ⁺ type composite perfluorosulfonate polymer membrane by hot pressing to prepare a composite polymer membrane / electrode assembly for a polymer fuel cell.

Figure 2 is a cross-sectional view of the composite membrane / electrode assembly produced through the above manufacturing process. In FIG. 2, the central portion is an ion exchange polymer membrane 3 and the layers formed on the upper and lower portions thereof are the anode and cathode catalyst layers 1, 2. In the composite polymer membrane / electrode assembly according to the present invention, there is a technical feature in the configuration in which the porous PTFE membrane 4 composited in the center of the polymer membrane 3 in the center is located.

The porous PTFE membrane (4) was prepared so as to be located exactly in the center of the polymer membrane as intended in the present invention. The ion exchange polymer membrane 3 is composed of a porous polymer membrane without pores that is tightly packed in the pores of the porous PTFE membrane 4.

3 is a scanning electron micrograph of a cross section of a single membrane / electrode assembly manufactured by the above manufacturing process. In the photograph of FIG. 3, the central portion is a polymer membrane and the layers formed on the upper and lower portions thereof are an electrode catalyst layer. The thickness of the catalyst layer is at most 15 μm and the thickness of the polymer membrane is at most 110 μm. It can be seen from FIG. 3 that the porous electrode catalyst layer is uniformly and continuously bonded to the polymer membrane having no pores, and also there are no signs of delamination at the interface.

Figure 4 is a scanning electron micrograph of the cross section of the composite membrane / electrode assembly produced through the above manufacturing process. In the photograph of Fig. 4, the central portion is a polymer membrane and the layers formed on the upper and lower portions thereof are electrode catalyst layers, and the thickness of the catalyst layer and the thickness of the polymer membrane are almost similar to those of Fig. 3. However, in FIG. 4, the composite porous PTFE membrane is located in the middle of the polymer membrane at the center, which is different from FIG. 3.

The porous PTFE membrane is precisely positioned in the center of the polymer membrane as intended in the present invention, and when the expanded PTFE membrane portion located in the center of the membrane is enlarged, the polymer membrane is densely filled in the pores of the porous PTFE membrane, so that the pores It was found that the composite polymer membrane was not prepared.

In addition, it can be seen that the electrode bonded to the composite polymer film also forms a uniform interface and is well bonded in succession, and no sign of delamination appears at the interface. The observation on the surface shows that the electrocatalyst layer forms a porous structure, and the uniform pore-distribution of porous Pt / C agglomerates is in close proximity to each other. there was.

In order to evaluate and evaluate the performance of the composite polymer membrane / electrode assembly obtained by the present invention, various polymer membrane / electrode assemblies were prepared and their performance was measured in a single cell.

To this end, a single polymer membrane which was not complexed with the composite polymer membrane in which the porous PTFE membrane was complexed was prepared, and a polymer membrane / electrode assembly was prepared according to the above process. In addition, to compare the performance of the composite polymer membrane prepared in the present invention with a commercial membrane, the same electrode was attached to the Nafion 115 membrane to prepare a Nafion polymer membrane / electrode assembly, which was used for performance evaluation.

In order to evaluate the performance of the polymer membrane / electrode assembly, first, the polymer membrane / electrode assembly was inserted between two gaskets, and then teflonized carbon cloth was placed on both sides of the polymer membrane / electrode assembly. The Teflon-treated carbon cloth serves to support the polymer membrane / electrode assembly as well as provide a hydrophobic distribution network that is appropriately dispersed to diffuse the gas reacting with the polymer membrane / electrode assembly. The assembly was inserted between two carbon plates having a gas outlet and an eve channel and then pressed between two copper end-plates to produce a unit cell. The active electrode area of the unit cell was 50 cm ² .

The fuel cell test apparatus used for the performance measurement was equipped with a plurality of thermostats, a flow meter and an external humidifier, and an electronic load having a maximum allowable limit of 3 kW was used for the performance evaluation of the unit cell.

FIG. 5 is a graph showing unit cell performance of a polymer membrane / electrode assembly prepared using a single membrane or a composite membrane and a 20 weight ratio Pt / C catalyst. The performance of the unit cell was measured at a temperature of 80 ° C. while supplying hydrogen and oxygen at a pressure of 1 atm for the anode and the cathode electrodes.

The polymer membrane / electrode assembly made of a single membrane exhibited a current density of 0.58 A / cm ² at a cell voltage of 0.6 V. When the composite polymer membranes 1 and 2 were used, 0.62 A / cm ² and 0.46 A / A current density of cm ² is shown. The polymer membrane / electrode assembly using the composite polymer membrane showed higher performance than the other polymer membrane / electrode assembly. The thickness of the single polymer membrane used for performance measurement was about 100 μm and the composite polymer membranes 1 and 2 were about 80 μm and 120 μm, respectively. The thickness of the composite polymer membrane 1 was the thinnest and the composite polymer membrane 2 was about the same as that of Nafion 115.

Considering the thickness of the polymer membrane, the performance of the polymer membrane / electrode assembly using the composite polymer membrane was similar to that of the polymer membrane / electrode assembly made of a single membrane. Since the porous PTFE membrane has a high porosity of 80 to 90%, it is judged that the porous PTFE membrane inserted into the polymer membrane does not significantly affect the performance degradation of the polymer membrane / electrode assembly using the composite polymer membrane.

FIG. 6 shows the performance of the polymer membrane / electrode assembly using the composite polymer membrane 2 and the Nafion 115 membrane, respectively, in both cases using 20 wt% Pt / C as the catalyst and hydrogen and oxygen as the reaction gas. This is the performance obtained by measuring at 1 atmosphere. The polymer membrane / electrode assembly using the composite polymer membrane 2 and the Nafion 115 membrane, respectively, had a current density of 0.46 A / cm ² and 0.56 A / cm ² at a battery voltage of 0.6 V and 0.3 A / cm ² and 0.31 A / at 0.7 V, respectively. A current density of cm ² is shown. As can be seen in FIG. 7, the performance of the polymer membrane / electrode assembly using the Nafion 115 membrane of the polymer membrane / electrode assembly using the composite polymer membrane 2 is almost the same in the high current density region, and does not show much difference in the low current density region. Could.

The composite membrane prepared by casting a Nafion solution on a porous support material has a higher gas permeability than conventional Nafion membranes, and has more reactant or oxidant crossovers in the fuel cell. The problem of intermixing has been pointed out. Therefore, the polymer membrane / electrode assembly of the composite membrane prepared by casting Nafion solution on the porous support material is considerably lower than the performance of the polymer membrane / electrode assembly using a common commercial membrane. However, the performances of composite polymer membranes made of porous PTFE membrane and perfluorosulfonylfluoride copolymer resin and polymer membrane / electrode assembly using Nafion 115 polymer membrane were similar. Therefore, it was confirmed that the composite molecular membrane and the composite polymer membrane / electrode assembly obtained by the present invention can be used for a polymer fuel cell.

As described above, according to the present invention, the hot pressing or rolling treatment causes the preform precursor film to melt on its surface. As a result, the molten preform precursor is embedded into the pores of the PTFE membrane. Since the enteric preform precursor and the PTFE membrane form a fully bonded composite polymer membrane, the gas permeability is lower and the crossover of the reactive fuel or the oxidant is lower than that of the polymer membrane prepared by casting a Nafion solution on a conventional porous support material. (reactants crossover) is less, there is an advantage that can solve the problem that they are intermixed in the fuel cell to reduce the fuel cell performance.

In addition, according to the manufacturing method of the composite polymer membrane according to the present invention, it is possible to reduce the price of the expensive polymer membrane used as the membrane of the polymer fuel cell, to produce a very thin electrolyte polymer membrane, and to reduce the expansion and contraction of the polymer membrane Mechanical properties can be obtained, and the manufacturing process is simpler, and manufacturing costs and manufacturing time can be shortened, compared with the conventional method for producing a composite polymer membrane using Nafion solution.

Claims (9)

Pre-formed precursor sheet by hot pressing or rolling process of perfluorosulfonylfluoride / TFE copolymer resin at a temperature of 200-250 ° C Molding), Inserting a porous membrane in the middle of the preform precursor sheet and the surface of the preform precursor membrane is melted by hot pressing or rolling at a temperature of 200 ~ 250 ℃ to embed the molten preform precursor membrane into the pores of the porous membrane To form the preform precursor and the porous membrane into a fully bonded composite sheet, The composite sheet was treated in an aqueous solution of caustic soda at a ratio of 5 to 30% by weight to prepare a composite preform sheet composed of the composite perfluorosulfonyl fluoride / TF copolymer resin in the form of Na ⁺ composite perfluorosulfonate polymer. membrane), A polymer fuel comprising the step of converting the composite perfluorosulfonate polymer membrane in Na ⁺ form into a composite perfluorosulfonate polymer membrane in H ⁺ form by additional hydration in 0.1-1 M sulfuric acid aqueous solution. Method for producing a composite polymer membrane for batteries. The powder of claim 1, wherein the perfluorosulfonyl fluoride / TF precursor resin consists of spherical particles having a particle size distribution of 20-200 μm or about 3.6 (L) x 2.4 (W) x 1.5 (T). Method for producing a composite polymer film for a polymer fuel cell, characterized in that the (mm) oval particles. The method of claim 1, wherein the porous membrane has a thickness of 15 to 100 µm, a pore size of 1 to 3 µm, and a porosity of 80 to 90%. Pre-formed precursor sheet by hot pressing or rolling process of perfluorosulfonylfluoride / TFE copolymer resin at a temperature of 200-250 ° C Molding), Inserting a porous membrane in the middle of the preform precursor sheet and the surface of the preform precursor membrane is melted by hot pressing or rolling at a temperature of 200 ~ 250 ℃ to embed the molten preform precursor membrane into the pores of the porous membrane To form the preform precursor and the porous membrane into a fully bonded composite sheet, The composite sheet was treated in an aqueous solution of caustic soda at a ratio of 5 to 30% by weight to prepare a composite preform sheet composed of the composite perfluorosulfonyl fluoride / TF copolymer resin in the form of Na ⁺ composite perfluorosulfonate polymer. membrane), Coating a platinum-based catalyst ink on the composite perfluorosulfonate polymer membrane in Na ⁺ form, and hot-pressurizing the composite polymer membrane coated with the catalyst ink at a temperature of 120 to 200 ° C. A method of manufacturing a composite polymer membrane / electrode assembly for a polymer fuel cell, characterized in that it comprises a step of manufacturing a composite (membrane polymer membrane / electrode assembly, MEA). 5. The method of claim 4, wherein after performing the final process, a process of additionally hydrating the composite polymer membrane / electrode assembly in a 0.1-1 M sulfuric acid aqueous solution to convert the composite polymer membrane into H ⁺ form into a composite perfluorosulfonate polymer membrane is carried out. A method for producing a composite polymer membrane / electrode assembly for a polymer fuel cell. The method of claim 4, wherein the catalyst ink is carbon (Pt / C, Pt-Ru / C) coated with platinum (Pt) and platinum (Pt)-ruthenium (Ru), Nafion solution, glycerol (tetra) and tetra Method for producing a composite polymer membrane / electrode assembly for a polymer fuel cell, characterized in that consisting of butyl ammonium hydroxide (TBAOH). The composite polymer membrane for polymer fuel cells according to claim 4, wherein the coating of the catalyst ink is performed by any one of a screen printing method, a spray method, or a doctor blade method. Method for producing an electrode assembly. Pre-formed precursor sheet by hot pressing or rolling process of perfluorosulfonylfluoride / TFE copolymer resin at a temperature of 200-250 ° C Molding), Inserting a porous membrane in the middle of the preform precursor sheet and the surface of the preform precursor membrane is melted by hot pressing or rolling at a temperature of 200 ~ 250 ℃ to embed the molten preform precursor membrane into the pores of the porous membrane To form the preform precursor and the porous membrane into a fully bonded composite sheet, The composite sheet was treated in an aqueous solution of caustic soda at a ratio of 5 to 30% by weight to prepare a composite preform sheet composed of the composite perfluorosulfonyl fluoride / TF copolymer resin in the form of Na ⁺ composite perfluorosulfonate polymer. membrane), Converting the composite perfluorosulfonate polymer membrane in Na ⁺ form into a composite perfluorosulfonate polymer membrane in H ⁺ form by additional hydration in 0.1-1 M sulfuric acid aqueous solution; A method of manufacturing a composite polymer membrane / electrode assembly for a polymer fuel cell, characterized in that the electrode is pressed to the H ⁺ type composite perfluorosulfonate polymer membrane by hot pressing. The method of claim 8, wherein the electrode, A catalyst slurry made of platinum (Pt) and platinum (Pt) -ruthenium (Ru) coated carbon powder (Pt / C, Pt-Ru / C), Teflon (PTFE) solution, crosslinking agent and peptizing agent is waterproofed as electrode support Uniformly coating on one carbon paper or carbon cloth by screen printing, spraying or doctor blade method; Drying the coated electrode in an inert gas atmosphere at 200 to 250 캜; A method of manufacturing a composite polymer membrane / electrode assembly for a polymer fuel cell, characterized in that the dried electrode is manufactured through a process of sintering for 10 to 50 minutes in an inert gas atmosphere at 300 to 370 ° C.