KR20070076284A - Cathode catalyst for fuel cell, manufacturing method thereof, membrane-electrode assembly and fuel cell system for fuel cell comprising same - Google Patents

Abstract

A cathode catalyst for a fuel cell, a method for manufacturing the same, a membrane-electrode assembly for the fuel cell comprising the same, and a fuel cell system are provided to improve the performances of the membrane-electrode assembly and the fuel cell system. A cathode catalyst comprises a carbon-based material and Ru-In-Ch supported on the carbon-based material, wherein Ch is a material selected from a group consisting of S, Se, and Te. A membrane-electrode assembly(131) for a fuel cell comprises an anode(3) and a cathode(5) positioned to face each other, and a polymer electrolytic membrane(1) positioned between the anode and the cathode. The cathode includes the cathode catalyst.

Description

Cathode catalyst for fuel cell, method for manufacturing the same, membrane-electrode assembly and fuel cell system for fuel cell comprising the same TECHNICAL CELL SYSTEM COMPRISING SAME AND FUEL CELL COMPRISING SAME AND FUEL CELL SYSTEM COMPRISING SAME }

1 is a view schematically showing a cross section of a membrane-electrode assembly for a fuel cell according to an embodiment of the present invention.

2 schematically illustrates the structure of a fuel cell system according to an embodiment of the invention.

3 is a graph showing the results of catalyst activity measured using Rotating Disk Electrode (RDE) of a fuel cell using a cathode catalyst for fuel cells prepared according to Example 1 and Comparative Example 1 of the present invention.

Figure 4 is a graph showing the X-ray diffraction peaks of the cathode catalyst prepared according to Example 1 of the present invention.

[Industrial use]

The present invention relates to a cathode catalyst for a fuel cell, a method of manufacturing the same, a membrane-electrode assembly for a fuel cell including the same, and a fuel cell system including the same, and more particularly, has excellent activity and selectivity for a reduction reaction of an oxidant, and The present invention relates to a fuel cell cathode catalyst and a method for manufacturing the same, a fuel cell membrane electrode assembly and a fuel cell system including the same.

[Prior art]

A fuel cell is a power generation system that converts chemical reaction energy of hydrogen and oxidant contained in hydrogen or hydrocarbon-based material directly into electrical energy.

Representative examples of the fuel cell include a polymer electrolyte fuel cell (PEMFC) and a direct oxidation fuel cell (Direct Oxidation Fuel Cell). When methanol is used as a fuel in the direct oxidation fuel cell, it is called a direct methanol fuel cell (DMFC).

In general, polymer electrolyte fuel cells have the advantages of high energy density and high output, but they require attention to the handling of hydrogen gas and fuels for reforming methane, methanol and natural gas to produce hydrogen, fuel gas. There is a problem that requires additional equipment such as a reforming device.

On the other hand, the direct oxidation type fuel cell has a lower reaction speed than the polymer electrolyte type due to the slower reaction rate, which requires a large amount of electrode catalyst, but it is easy to handle liquid fuel and the operating temperature is high. It has the advantage of being low and in particular not requiring a fuel reformer.

In such a fuel cell system, the stack that substantially generates electricity is comprised of several to several dozen unit cells consisting of a membrane-electrode assembly (MEA) and a separator (or bipolar plate). It has a laminated structure. The membrane-electrode assembly is called an anode electrode (also called "fuel electrode" or "oxide electrode") and a cathode electrode (also called "air electrode" or "reduction electrode") with a polymer electrolyte membrane including a hydrogen ion conductive polymer therebetween. Has a bonded structure.

It is an object of the present invention to provide a cathode catalyst for a fuel cell having excellent activity and selectivity for the reduction reaction of an oxidant.

Another object of the present invention is to provide a method for preparing the cathode catalyst.

Yet another object of the present invention is to provide a membrane-electrode assembly for a fuel cell comprising the cathode catalyst.

Still another object of the present invention is to provide a fuel cell system comprising the membrane-electrode assembly for a fuel cell of the present invention.

In order to achieve the above object, the present invention is a fuel cell comprising a carbon-based material and Ru-In-Ch (Ch is one element selected from the group consisting of S, Se and Te) supported on the carbon-based material It provides a cathode catalyst.

The present invention also prepares a first mixture by mixing a carbonaceous material powder, a ruthenium-containing material, an indium-containing material and a solvent, and a second mixture by mixing the first mixture, the chalcogen element-containing material and the solvent. And it provides a method for producing a cathode catalyst for a fuel cell comprising the step of calcining the second mixture.

The present invention also includes an anode electrode and a cathode electrode positioned to face each other and a polymer electrolyte membrane positioned between the anode and the cathode electrode, the anode electrode and the cathode electrode comprises a conductive electrode substrate and a catalyst layer formed on the electrode substrate It includes, and the catalyst layer of the cathode electrode provides a membrane-electrode assembly for a fuel cell comprising the cathode catalyst of the present invention.

The present invention also provides an electricity generator including the membrane electrode assembly of the present invention and separators located on both sides of the membrane electrode assembly, a fuel supply unit supplying fuel to the electricity generator, and an oxidant to the electricity generator. It provides a fuel cell system comprising an oxidant supply.

Hereinafter, the present invention will be described in more detail.

A fuel cell is a power generation system that obtains electrical energy through oxidation of a fuel and reduction of an oxidant. An oxidation reaction of a fuel occurs at an anode electrode and a reduction reaction of an oxidant occurs at a cathode electrode.

Catalysts capable of promoting the oxidation reaction of the fuel and the reduction reaction of the oxidant are used for the catalyst layers of the anode electrode and the cathode electrode, and platinum-ruthenium is typically used for the catalyst layer of the anode electrode and platinum is used for the catalyst layer of the cathode electrode.

However, the platinum used as the cathode catalyst lacks the selectivity for the reduction reaction of the oxidant, and is depolarized by the fuel passing through the electrolyte membrane to the cathode region in a direct oxidation fuel cell. There is a problem that is deactivated, attention is focused on the catalyst that can replace platinum.

The cathode catalyst of the present invention is to solve the above problems, the Ru-In-Ch (Ch is one element selected from the group consisting of S, Se and Te) supported on the carbon-based material and the carbon-based material Include. In the catalyst, Ru-In-Ch is an active material having activity for the reduction reaction of an oxidant, and the carbon-based material corresponds to a carrier supporting the Ru-In-Ch.

In Ru-In-Ch as an active substance, ruthenium (Ru) is a platinum-based element and has a high activity for the reduction reaction of the oxidant. However, oxygen in the air is easily adsorbed to ruthenium, which makes the reduction reaction of the oxidant difficult by blocking the active center of ruthenium where the reduction reaction of the oxidant occurs.

Chalcogen elements such as sulfur (S), selenium (Se), and telelium (Te) combine with ruthenium to prevent oxygen in the air from adsorbing to ruthenium, thereby ruthenium is selective for the reduction of oxidant as described above. To indicate activity.

The indium (In) further increases the catalytic activity of ruthenium. This is because indium has electrons in the p-orbital of the outermost electron shell as a typical metal element of 5-cycle group 13, and these electrons can be easily transferred to ruthenium.

As a result, the active material Ru-In-Ch has excellent activity and selectivity for the reduction reaction of the oxidizing agent can be effectively used as a cathode catalyst for fuel cells. In particular, due to the excellent selectivity to the reduction reaction of the oxidant, it can be used more effectively in a direct oxidation fuel cell in which crossover of fuel is a problem.

In the Ru-In-Ch, the ruthenium, indium and chalcogen content is preferably 40-60 atomic% ruthenium, 30-35 atomic% indium and 5-30 atomic% chalcogen. . If ruthenium is lower than 40 atomic% or higher than 60 atomic%, and also if indium is lower than 30 atomic% or higher than 35 atomic%, the crystallinity is increased so much that the activity is lowered, which is not preferable. In addition, when the chalcogen element is less than 5 atomic%, oxygen is prevented from adsorbing to ruthenium, that is, it cannot protect the active site, and when it exceeds 30 atomic%, the content of the chalcogen element is so high that both active sites It is not preferable because it is covered with a chalcogen element and the activity is lowered.

The Ru-In-Ch may be formed not only crystalline but also amorphous. The cathode catalyst of the present invention preferably includes both crystalline Ru-In-Ch and amorphous Ru-In-Ch. That is, a state in which crystalline Ru-In-Ch and amorphous Ru-In-Ch are mixed is preferable, which generates a large number of defects at the boundary between crystalline and amorphous, and active sites Because there may be more.

The Ru-In-Ch is used by being supported on a carbon-based material. This is because when Ru-In-Ch is used by itself, there is a problem in that the electrical conductivity is insufficient and particles are agglomerated with each other to obtain particles of small size. By supporting the carbon-based material, the electrical conductivity of the catalyst can be improved, and the size of the catalyst particles can be reduced to increase the surface area per unit mass, that is, the specific surface area. By increasing the specific surface area, the activity per unit mass of the catalyst can be increased.

Any carbon-based material may be used as the carrier, but graphite, denka black, ketjen black, carbon nanotubes, carbon nanofibers, carbon nanowires, carbon nano-horns, and carbon nano-balls ) May be preferably used.

The particle size of the carbon-based material powder does not have a great influence on the effects of the present invention and may be appropriate level. However, since the particle size of the catalyst including the Ru-In-Ch-supported carbon-based material affects the catalytic activity and stability, it is preferable to have a catalyst particle diameter of 2 to 3 nm in consideration of stability and catalyst activity.

The amount of the Ru-In-Ch supported on the carbon-based material is preferably 5 to 90% by weight, more preferably 20 to 80% by weight based on the total weight of the catalyst. If the supported amount is less than 5% by weight, there is a problem that the activity per mass of the catalyst falls too much, and if it exceeds 90% by weight, the Ru-In-Ch is excessively excessive, which is not preferable because the activity may be reduced.

The present invention also provides a method for producing a cathode catalyst for a fuel cell. The production method can further improve the catalytic activity by forming both crystalline and amorphous Ru-In-Ch in the catalyst.

In the method for preparing a cathode catalyst for a fuel cell of the present invention, a carbon-based powder, a ruthenium-containing material, an indium-containing material, and a solvent are mixed to prepare a first mixture, and the first mixture, the chalcogen element-containing material, and the solvent are prepared. Mixing to prepare a second mixture, and calcining the second mixture.

Hereinafter, each step will be described in detail.

First, a first mixture is prepared by mixing a carbonaceous material powder, a ruthenium-containing material, an indium-containing material, and a solvent. Graphite, denka black, ketjen black, carbon nanotubes, carbon nanofibers, carbon nanowires, carbon nanohorn or carbon nanoballs may be preferably used as the carbonaceous material in the preparation of the first mixture. In addition, the ruthenium-containing material is preferably water-soluble and includes ruthenium, and examples thereof include ruthenium chloride, ruthenium acetylacetonate, or ruthenium nitrozylnitrate. have. In addition, the indium-containing material preferably has water solubility and includes indium, and representative examples thereof include indium chloride. In addition, water, ethanol or methanol may be preferably used as the solvent.

When the first mixture is prepared as described above, a process of drying the first mixture may be performed. The drying is preferably carried out in a vacuum state, the drying temperature is preferably 150-300 ℃. This drying step causes the solvent to evaporate and form a black powder.

The second mixture is prepared by mixing the first mixture, the chalcogen element-containing material and the solvent with a solvent. As the solvent, water, methanol or ethanol may be used as in the preparation of the first mixture.

As the chalcogen element-containing material, any compound or salt containing Se, S or Te may be used, and representative examples thereof include selenic acid (Selenious acid, H ₂ SeO ₃ ).

Finally, the catalyst powder may be obtained by calcining the second mixture. The calcination step is preferably carried out at a temperature of 200-300 ℃ in a reducing atmosphere. The reducing atmosphere may be a hydrogen atmosphere or a mixed atmosphere of N ₂ / H ₂ (about 1: 1 volume ratio).

Through the preparation method, a catalyst including Ru-In-Ch supported on a carbon-based material and a carbon-based material may be prepared, and crystalline Ru-In-Ch and amorphous Ru-In-Ch coexist in the catalyst. It can show more improved activity.

The present invention also provides a fuel cell membrane-electrode assembly comprising the cathode catalyst for fuel cell of the present invention as described above.

The membrane-electrode assembly of the present invention includes an anode electrode and a cathode electrode positioned to face each other and a polymer electrolyte membrane positioned between the anode and the cathode electrode, wherein the anode electrode and the cathode electrode are formed of an electrode substrate and a conductive substrate. It includes a catalyst layer formed on the electrode substrate.

1 is a view schematically showing a cross section of the membrane-electrode assembly 131 according to an embodiment of the present invention. Hereinafter, the membrane-electrode assembly 131 of the present invention will be described with reference to the drawings.

The membrane-electrode assembly 131 is a portion that generates electricity through oxidation of fuel and reduction of oxidant, and one or several are stacked to form a stack.

A reduction reaction of the oxidant occurs in the catalyst layer 53 of the cathode electrode, and the catalyst layer includes the cathode catalyst for fuel cell of the present invention. The cathode catalyst shows excellent activity and selectivity for the reduction reaction of the oxidant, thereby improving the performance of the cathode electrode 5 and the membrane-electrode assembly 131 including the same.

In the catalyst layer 33 of the anode electrode, an oxidation reaction of fuel occurs, and a catalyst capable of promoting this may be included. A platinum-based catalyst, which is conventionally used, may be used. The platinum-based catalyst may be platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy or platinum-M alloy (M is Ga, Ti, V, Cr, Mn, Fe, Co, Ni, At least one catalyst selected from the group consisting of Cu and Zn, and at least one transition metal selected from the group consisting of Cu and Zn.

The anode electrode catalyst may be used as the catalyst itself (black), or may be supported on a carrier. As the carrier, carbon such as acetylene black, denka black, activated carbon, ketjen black, graphite may be used, or inorganic fine particles such as alumina, silica, titania, zirconia may be used, but carbon may be most preferably used. have.

Catalyst layers 33 and 53 of the anode electrode and the cathode electrode may include a binder. As the binder, any material generally used in an electrode for a fuel cell may be used, and representative examples thereof include polytetrafluoroethylene, Polyvinylidene fluoride, polyvinylidene chloride, polyvinyl alcohol, cellulose acetate, poly (perfluorosulfonic acid) and the like can be used.

The electrode substrates 31 and 51 of the anode electrode and the cathode electrode serve to make a reaction source, that is, a fuel and an oxidant, easily accessible to the catalyst layers 31 and 51, and the electrode substrates 31 and 51 are conductive. The surface of a fabric formed of a porous film or polymer fiber composed of carbon paper, carbon cloth, carbon felt or metal cloth (fibrous metal cloth) The metal film is formed on (metalized polymer fiber)) may be used, but is not limited thereto.

As the polymer electrolyte membrane 1, a polymer having an ion exchange function of transferring hydrogen ions generated in the catalyst layer 33 of the anode electrode to the catalyst layer 53 of the cathode electrode, and having excellent hydrogen ion conductivity may be used.

Representative examples thereof include a polymer resin having a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups and derivatives thereof in the side chain.

Representative examples of the polymer resin include fluorine polymer, benzimidazole polymer, polyimide polymer, polyetherimide polymer, polyphenylene sulfide polymer, polysulfone polymer, polyether sulfone polymer, polyether ketone It may include one or more selected from the group polymer, polyether-ether ketone-based polymer or polyphenylquinoxaline-based polymer, more preferably poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid ), Copolymers of tetrafluoroethylene and fluorovinyl ether containing sulfonic acid groups, defluorinated sulfide polyether ketones, aryl ketones, poly (2,2'-m-phenylene) -5,5'-bi Benzimidazole (poly (2,2 '-(m-phenylene) -5,5'-bibenzimidazole) or poly (2,5-benzimidazole) may be used. Electrolyte membrane is 10-200㎛ Has a thickness.

In addition, the cathode and anode electrodes may further include a microporous layer for enhancing the diffusion effect of the reactants on the electrode substrate. This microporous layer may generally comprise a conductive powder having a small particle diameter, such as carbon powder, carbon black, acetylene black, activated carbon, carbon fiber, fullerene or carbon nanotubes.

The microporous layer is prepared by coating a composition comprising a conductive powder, a binder resin and a solvent on the electrode substrate. As the binder resin, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, cellulose acetate, and the like may be preferably used. The solvent may be ethanol, isopropyl alcohol, n-propyl alcohol, butyl alcohol, or the like. Alcohols, water, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and the like can be preferably used. The coating process may be a screen printing method, a spray coating method or a coating method using a doctor blade according to the viscosity of the composition, but is not limited thereto.

The process of manufacturing the electrode of the present invention having such a configuration can be carried out by the process of forming a catalyst layer on the electrode substrate using a conventional method such as spray coating, doctor blade, and the like, the catalyst composition comprising a catalyst, a binder and a solvent. Since the electrode manufacturing process is well known in the art, detailed description thereof will be omitted.

The present invention also provides a fuel cell system comprising the membrane-electrode assembly of the present invention as described above. The fuel cell system of the present invention includes at least one electricity generating portion, a fuel supply portion and an oxidant supply portion.

The electricity generating unit includes the membrane-electrode assembly of the present invention and a separator (bipolar plate) located on both sides of the membrane-electrode assembly. The electricity generation unit serves to generate electricity through the oxidation reaction of the fuel and the reduction reaction of the oxidant.

The fuel supply unit serves to supply fuel to the electricity generation unit, and the oxidant supply unit serves to supply an oxidant to the electricity generation unit. The fuel means hydrogen or hydrocarbon fuel in gas or liquid state, and typical hydrocarbon fuels include methanol, ethanol, propanol or butanol, and the like. Oxygen is typically used as the oxidant, and may be used by injecting pure oxygen or air. However, the fuel and the oxidant are not limited thereto.

The fuel cell system of the present invention may be employed without limitation in Polymer Electrolyte Membrane Fuel Cell (PEMFC) and Direct Oxidation Fuel Cell (PEMFC). However, since the selectivity to the oxygen reduction reaction of the catalyst used in the catalyst layer of the cathode electrode is excellent, it can be used more effectively in a direct oxidized fuel cell in which crossover of fuel is problematic, and a direct methanol fuel cell (DMFC: Direct Methanol) Fuel Cell) can be used most effectively.

A schematic structure of a fuel cell system 100 according to an embodiment of the present invention is shown in FIG. 2, which will be described in more detail with reference to the following. 2 shows a system for supplying fuel and oxidant to the electricity generating unit 130 using pumps 151 and 171, but the fuel cell membrane-electrode assembly 131 of the present invention is limited to such a structure. Of course, it can be used in a fuel cell system having a structure using a diffusion method without using a pump.

The fuel cell system 100 includes a stack 110 having at least one electricity generator 130 for generating electrical energy through an oxidation reaction of a fuel and a reduction reaction of an oxidant, and a fuel supply unit 150 for supplying the fuel. ) And an oxidant supply unit 170 for supplying an oxidant to the electricity generating unit 130.

The fuel supply unit 150 supplying the fuel includes a fuel tank 153 for storing fuel and a fuel pump 151 connected to the fuel tank 153. The fuel pump 151 serves to discharge the fuel stored in the fuel tank 153 by a predetermined pumping force.

The oxidant supply unit 170 for supplying an oxidant to the electricity generating unit 130 of the stack 110 includes at least one oxidant pump 171 that sucks the oxidant with a predetermined pumping force.

The electricity generating unit 130 is a membrane-electrode assembly 131 for oxidizing and reducing a fuel and an oxidant and a separator (bipolar plate) 133 and 135 for supplying fuel and an oxidant to both sides of the membrane-electrode assembly 131. It is composed of

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples.

(Example 1)

To 5 ml of water, 1 g of graphite powder, 2.5 g of ruthenium chloride and 1.7 g of indium chloride were mixed for 2 hours, and dried at 80 ° C. The dried product obtained was dried in a vacuum oven at a temperature of 200 ° C. for 24 hours to obtain black powder.

1 g of the black powder and 0.21 g of selenious acid (S 2 SeO 3) were mixed in 5 ml of water, and dried at 80 ° C. The dried product was then dried in a vacuum oven at a temperature of 200 ° C. for 24 hours and calcined at 250 ° C. for 3 hours in a hydrogen atmosphere to comprise Ru 55 atomic%, In 35 atomic% and Se 10 atomic% , A cathode catalyst for a fuel cell having a loading of 50% by weight of Ru-In-Se was prepared.

(Example 2)

The same procedure as in Example 1 was conducted except that the amount of ruthenium chloride, indium chloride, and selenic acid was changed to prepare a cathode catalyst for a fuel cell including 40 atomic% of Ru, 30 atomic% of In, and 5 atomic% of Se. It was.

(Comparative Example 1)

0.6 g of ruthenium chloride, 0.03 g of selenious acid (H 2 SeO 3), and 1 g of carbon were dissolved in 150 ml toluene, and then mixed at 140 ° C. for 24 hours. The mixture was filtered, dried at 90 ° C., and calcined at 250 ° C. for 3 hours to produce a cathode catalyst powder for fuel cell.

The catalytic activity of the catalysts prepared according to Example 1 and Comparative Example 1 was measured by Rotating Disk Electrode (RDE). In the RDE measurement, Ag / AgCl was used as the reference electrode and Pt was used as the counter electrode, and oxygen gas was saturated by bubbling oxygen gas in a 0.5 M sulfuric acid solution for 2 hours. Using a sulfuric acid solution, it was measured at a scan rate of 10 mV / s, a rotating speed of 2000 rpm. The results are shown in FIG. As shown in Figure 3, it can be seen that the catalyst of Example 1 is superior to the catalytic activity compared to Comparative Example 1. In addition, the same results as in Example 1 were obtained when the same experiment was conducted using the catalyst of Example 2.

In addition, X-ray diffraction peaks of the catalyst prepared according to Example 1 were measured and the results are shown in FIG. 4. X-ray diffraction peaks were measured using CuK rays. As shown in FIG. 4, it can be seen that the crystallinity is low because the X-ray diffraction peaks of the catalyst of Example 1 are not sharp.

The cathode catalyst for a fuel cell of the present invention is excellent in activity and selectivity for a reduction reaction of an oxidant, and has an advantage of improving performance of a fuel cell membrane-electrode assembly and a fuel cell system including the same.

Claims (20)

Carbon-based materials; And A cathode catalyst for a fuel cell comprising Ru-In-Ch (Ch is one element selected from the group consisting of S, Se, and Te) supported on the carbonaceous material. The method of claim 1, The content of Ru in the Ru-In-Ch is 40 to 60 atomic%, the content of In is 30 to 35 atomic%, the content of Ch is 5 to 30 atomic% of the cathode catalyst for fuel cells. The method of claim 1, The loading amount of the Ru-In-Ch is 5 to 90% by weight based on the total weight of the catalyst cathode catalyst for fuel cells. The method of claim 3, The supported amount of Ru-In-Ch is 20 to 80% by weight relative to the total weight of the catalyst cathode catalyst for fuel cells. The method of claim 1, The carbon-based material is a cathode catalyst for a fuel cell is selected from the group consisting of graphite, denka black, ketjen black, carbon nanotubes, carbon nanofibers, carbon nanowires, carbon nanohorns and carbon nanoballs. The method of claim 1, The cathode catalyst for fuel cell is a fuel cell cathode catalyst comprising crystalline Ru-In-Ch and amorphous Ru-In-Ch. Preparing a first mixture by mixing a carbonaceous material, a ruthenium-containing material, an indium-containing material, and a solvent, Mixing the first mixture, the chalcogen element-containing material and the solvent to prepare a second mixture, Calcining the second mixture Method for producing a cathode catalyst for a fuel cell comprising the step. The method of claim 7, wherein The carbon-based material is graphite, denka black, ketjen black, carbon nanotubes, carbon nanofibers, carbon nanowires, carbon nanohorns and carbon nanoballs is a method for producing a cathode catalyst for a fuel cell. The method of claim 7, wherein The ruthenium-containing material is a method for producing a cathode catalyst for a fuel cell is selected from the group consisting of ruthenium chloride, ruthenium acetylacetonate and ruthenium nitrozylnitrate. The method of claim 7, wherein The indium-containing material is a method of producing a cathode catalyst for a fuel cell that is indium chloride (indium chloride). The method of claim 7, wherein The solvent is a method of producing a cathode catalyst for a fuel cell is selected from the group consisting of water, ethanol and methanol. The method of claim 7, wherein The drying step is a method of producing a cathode catalyst for a fuel cell that is carried out in a vacuum and at a temperature of 150 to 300 ℃. The method of claim 7, wherein The calcining step is a method of producing a cathode catalyst for a fuel cell that is carried out at a temperature of 200 to 300 ℃. An anode electrode and a cathode electrode located opposite each other; And A polymer electrolyte membrane positioned between the anode and the cathode electrode, The cathode electrode is formed on the conductive electrode substrate and the electrode substrate, comprising a cathode catalyst according to any one of claims 1 to 6. Membrane-electrode assembly for fuel cell. The method of claim 14, The polymer electrolyte membrane comprises a polymer resin having a cation exchange group selected from the group consisting of sulfonic acid group, carboxylic acid group, phosphoric acid group, phosphonic acid group and derivatives thereof in the side chain. The method of claim 15, The polymer resin may be a fluorine-based polymer, benzimidazole-based polymer, polyimide-based polymer, polyetherimide-based polymer, polyphenylene sulfide-based polymer, polysulfone-based polymer, polyethersulfone-based polymer, polyetherketone-based polymer, poly Membrane-electrode assembly for fuel cell, which is at least one polymer resin selected from the group consisting of ether-etherketone-based polymers and polyphenylquinoxaline-based polymers. The method of claim 16, The polymer resin is tetrafluoroethylene containing poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), sulfonic acid group. Copolymers of fluorovinyl ethers containing sulfonic acid groups, defluorinated sulfide polyether ketones, aryl ketones, poly (2,2'-m-phenylene) -5,5'-bibenzimidazoles (poly (2 Membrane-electrode assembly for fuel cell, which is at least one polymer resin selected from the group consisting of 2,5- (m-phenylene) -5,5'-bibenzimidazole) and poly (2,5-benzimidazole). An electricity generator comprising a membrane electrode assembly according to claim 14 and a separator located on both sides of the membrane electrode assembly; A fuel supply unit supplying fuel to the electricity generation unit; And A fuel cell system comprising an oxidant supply unit for supplying an oxidant to the electricity generation unit. The method of claim 18, The fuel cell system is selected from the group consisting of a polymer electrolyte fuel cell and a direct oxidation fuel cell. The method of claim 19, And the fuel cell system is a direct oxidation fuel cell.

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