KR100717797B1 - Cathode catalyst for fuel cell, membrane-electrode assembly for fuel cell and fuel cell system comprising same - Google Patents

Abstract

The present invention relates to a cathode catalyst for a fuel cell, a membrane-electrode assembly and a fuel cell system for a fuel cell comprising the same, wherein the cathode catalyst is a carbon-based material and crystalline M ₁ -M ₂ -Ch and amorphous supported on the carbon-based material. M ₁ -M ₂ -Ch (M ₁ is a metal selected from the group consisting of Ru, Pt and Rh, M ₂ is a metal selected from the group consisting of W and Mo, Ch is a group consisting of S, Se and Te) Is a chalcogen element selected from).

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.

Fuel Cell, Electrode, Amorphous, Crystalline, M1-M2-Ch

Description

Cathode catalyst for fuel cell, membrane-electrode assembly and fuel cell system for fuel cell comprising same {CATHODE CATALYST FOR FUEL CELL, MEMBRANE-ELECTRODE ASSEMBLY FOR FUEL CELL 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 X-ray diffraction analysis of the catalyst prepared according to Example 1 of the present invention.

4 is a transmission electron microscopy (TEM) photograph of the catalyst of Example 1 of the present invention.

5 is a graph showing the current density according to the voltage change of the catalyst of Example 1 and Comparative Example 1 of the present invention.

[Industrial use]

The present invention relates to a cathode catalyst for a fuel cell, a fuel cell membrane-electrode assembly and a fuel cell system including the same, and more particularly, has an excellent activity and selectivity for a reduction reaction of an oxidant, and includes a membrane-electrode for a fuel cell including the same. A cathode catalyst capable of improving the performance of an assembly and a fuel cell system, and a membrane-electrode assembly for a fuel cell and a fuel cell system comprising 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. This fuel cell is a clean energy source that can replace fossil energy, and has the advantage of generating a wide range of outputs by stacking unit cells, and having an energy density of 4-10 times that of a small lithium battery. It is attracting attention as a compact and mobile portable power source.

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.

In contrast, the direct oxidation fuel cell has a slower reaction rate, which results in lower energy density, lower power, and a larger amount of electrode catalyst than the polymer electrolyte type, but it is easy to handle liquid fuel and has a low operating temperature. In particular, it has the advantage of not requiring a fuel reformer.

In such fuel cell systems, the stack that substantially generates electricity may comprise several to tens of 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 structure in which

The principle of generating electricity in a fuel cell is that fuel is supplied to an anode electrode, which is a fuel electrode, adsorbed to a catalyst of the anode electrode, and the fuel is oxidized to generate hydrogen ions and electrons. Reaching the cathode electrode, hydrogen ions pass through the polymer electrolyte membrane and are delivered to the cathode electrode. An oxidant is supplied to the cathode, and the oxidant, hydrogen ions, and electrons react on the catalyst of the cathode to generate electricity while producing water.

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.

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

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

In order to achieve the above object, the present invention is a carbon-based material and crystalline M ₁ -M ₂ -Ch and amorphous M ₁ -M ₂ -Ch supported on the carbon-based material (M ₁ is Ru, Pt and Rh group It is a metal selected from, M ₂ is a metal selected from the group consisting of W and Mo, Ch is a chalcogen element selected from the group consisting of S, Se and Te) provides a cathode catalyst for a fuel cell.

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 that has passed through the electrolyte membrane to the cathode region in a direct oxidation fuel cell. As a result, there is a problem of deactivation, and attention is focused on a catalyst that can replace platinum.

Cathode catalyst of the present invention is to solve the above problems, the carbon-based material and the crystalline M ₁ -M ₂ -Ch and amorphous M ₁ -M ₂ -Ch supported on the carbon-based material (M ₁ is Ru, A metal selected from the group consisting of Pt and Rh, M ₂ is a metal selected from the group consisting of W and Mo, and Ch is a chalcogen element selected from the group consisting of S, Se, and Te). It exhibits good activity and selectivity for the reduction of oxidants.

M ₁ is a metal selected from the group consisting of Ru, Pt, and Rh, and Ru, Pt, and Rh are platinum-based metal elements and exhibit high activity for the reduction reaction of the oxidant. However, oxygen in the air easily adsorbs to the metals to form an oxide, and this oxygen makes the reduction reaction of the oxidant difficult by blocking an active center of the metals in which the reduction reaction of the oxidant occurs.

Ch is a chalcogen element selected from the group consisting of S, Se, and Te, and S, Se, or Te combines with Ru, Pt, or Rh, and oxygen in the air adsorbs to Ru, Pt, or Rh to form an oxide. To prevent

M ₂ is a metal selected from the group consisting of W and Mo, where W or Mo provides electrons to Ru, Pt or Rh to enhance the activity of Ru, Pt or Rh.

As a result, M ₁ -M ₂ -Ch not only has a high activity for the reduction reaction of the oxidant, but also has excellent selectivity, so that the performance of the cathode can be maintained even if the fuel is crossover to the cathode.

In the M ₁ -M ₂ -Ch, the ratio of M ₁ and M ₂ is preferably 1 to 6 to 8. If the ratio of M ₁ and Ch is out of the above range, there is a problem in that the activity of the catalyst falls. Incidentally, the ratio of M ₁ and Ch is preferably 1 to 0.5 to 1. If the ratio of Ch to M ₁ is less than 0.5, the selectivity to the oxygen reduction reaction is inferior, and if the ratio of Ch to M ₁ exceeds 1, there is a problem that the catalytic activity is lowered.

In the cathode catalyst of the present invention, M ₁ -M ₂ -Ch includes both crystalline and amorphous, by including them together to improve the activity of the oxidizing agent for the reduction reaction.

This means that the surface energy of the active center in the region where the crystalline M ₁ -M ₂ -Ch and the amorphous M ₁ -M ₂ -Ch is in contact is about 10 to about 10 to the surface energy of the active center in the crystalline region. It is about 50 times higher, since the activity of the reduction reaction of the oxidant is much greater in the region where the crystalline and amorphous M ₁ -M ₂ -Ch contact.

The amorphous M ₁ -M ₂ -Ch preferably accounts for 20 to 80% by weight, more preferably 30 to 70% by weight, more preferably 40 to 60% by weight based on the total M ₁ -M ₂ -Ch. Even more preferred. When the ratio of amorphous exceeds 80% by weight, the M ₁ -M ₂ -Ch phase is not stable, and when it is less than 20% by weight, there is a problem that the activity of the catalyst is lowered, which is not preferable.

The M ₁ -M ₂ -Ch is used by itself to be supported on a carbon-based material in order to widen the specific surface area because the particles are agglomerated with each other to obtain a small particle size.

As the carbon-based material, graphite, denka black, ketjen black, acetylene black, activated carbon, carbon nanotubes, carbon nanofibers and carbon nanowires may be preferably used.

The cathode catalyst of the present invention described above dissolves the water-soluble salt of the metal M _{1 and} the water-soluble salt of the metal M ₂ in a solvent, mixes the carbonaceous material powder with the prepared solution, and then performs a first vacuum treatment and a first vacuum. The powder prepared by the treatment and the source of the chalcogen element may be added to the solvent, followed by a second vacuum treatment, and a heat treatment of the powder prepared by the second vacuum treatment. .

First, the water-soluble salt of metal M _{1 and} the water-soluble salt of metal M ₂ are dissolved in a solvent, and the carbonaceous material powder is mixed with the prepared solution. Ruthenium chloride, ruthenium acetylacetonate or ruthenium carbonyl may be used as the water-soluble salt of ruthenium in the water-soluble salt of metal M ₁ , and ammonium metatungstate may be used as the water-soluble salt of tungsten in the water-soluble salt of metal M ₂ . . Water, acetone or benzene may be used as the solvent. In addition, the materials described above may be preferably used as the carbon-based material.

Next, the mixture prepared in the mixing step is subjected to a first vacuum treatment. The primary vacuum treatment is preferably performed at a temperature of 100 to 300 ° C. for 1 to 24 hours in a vacuum state.

After the primary vacuum treatment, the source of the powder and chalcogen element obtained through the primary vacuum treatment is added to the solvent, followed by secondary vacuum treatment. Water, acetone or benzene may be preferably used as the solvent, and S powder, Se powder, Te powder, H ₂ SO ₃ , H ₂ SeO ₃ and H ₂ TeO ₃ may be preferably used as a source of the chalcogen element. Can be. The secondary vacuum treatment is preferably performed for 1 to 24 hours at a temperature of 100 to 300 ℃ in a vacuum state.

Finally, the powder obtained by the secondary vacuum treatment is heat treated. The heat treatment is preferably performed at a temperature of 200 to 350 ° C. for 3 to 6 hours in a hydrogen atmosphere.

Through the above process, the cathode catalyst for a fuel cell of the present invention including crystalline and amorphous M ₁ -M ₂ -Ch can be prepared.

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

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 on a conductive electrode substrate and the electrode substrate. It includes a catalyst layer formed.

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 generates electricity through oxidation of a fuel and reduction of an oxidant, and one or several are stacked and mounted in a stack.

A reduction reaction of the oxidant occurs in the catalyst layer 53 of the cathode electrode, and the catalyst layer includes a carbonaceous material and crystalline M ₁ -M ₂ -Ch and amorphous M ₁ -M ₂ -Ch supported on the carbonaceous material. A cathode catalyst for a fuel cell is included. 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 catalyst may be used as the catalyst itself (black) or may be used on a carrier. As the carrier, carbon-based materials such as graphite, denka black, ketjen black, acetylene black, activated carbon, carbon nanotube, carbon nanofiber and carbon nanowire may be used, or inorganic materials such as alumina, silica, titania, zirconia, and the like. Particulates may be used, but carbon-based materials may be most preferably used.

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 fluoride, 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 support the electrode, and serve to easily access a reaction source, that is, a fuel and an oxidant, to the catalyst layers 31 and 51. As the substrates 31 and 51, a conductive substrate is used, and representative examples thereof include carbon paper, carbon cloth, carbon felt, or metal cloth (porous film composed of metal in a fibrous state or The metal film is formed on the surface of the cloth formed of polymer fibers) may be used, but is not limited thereto.

In addition, it is preferable to use a water-repellent treatment with a fluorine-based resin as the electrode base material because it can prevent the reactant diffusion efficiency from being lowered by water generated when the fuel cell is driven. As the fluorine-based resin, polyvinylidene fluoride, polytetrafluoroethylene, fluorinated ethylene propylene, polychlorotrifluoroethylene, fluoroethylene polymer, or the like may be used.

In addition, a microporous layer may be further included to enhance the reactant diffusion effect in the electrode substrate. These microporous layers are generally conductive powders having a small particle diameter, such as carbon powder, carbon black, acetylene black, activated carbon, carbon fiber, fullerene, carbon nanotubes, carbon nanowires, and carbon nanohorns. -horn or carbon nano ring. 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. Alcohol, water, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and the like can be preferably used. The coating process may be screen printing, spray coating, or coating using a doctor blade according to the viscosity of the composition, 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 a fluorine polymer, a benzimidazole polymer, a polyimide polymer, a polyetherimide polymer, a polyphenylene sulfide polymer, a polysulfone polymer, a polyether sulfone polymer and a polyether ketone It may include at least one selected from a polymer, a polyether-etherketone-based polymer or a polyphenylquinoxaline-based polymer, more preferably poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), Copolymers of tetrafluoroethylene and fluorovinyl ethers containing sulfonic acid groups, defluorinated sulfided polyether ketones, aryl ketones, poly [2,2 '-(m-phenylene) -5,5'-bibenziimi 1 or more types chosen from polyazole (poly [2,2 '-(m-phenylene) -5,5'-bibenzimidazole]) or poly (2,5-benzimidazole). In general, the polymer electrolyte membrane has a thickness of 10 to 200㎛.

 In the hydrogen ion conductive group of the hydrogen ion conductive polymer, H may be substituted with Na, K, Li, Cs or tetrabutylammonium. In case of replacing H by Na in the ion-exchange group of the side chain terminal, NaOH is substituted in the preparation of the catalyst composition, and tetrabutylammonium hydroxide is used in the case of using tetrabutylammonium, and K, Li or Cs is also substituted with appropriate compounds. It can be substituted using. Since this substitution method 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 the fuel cell system 100 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 generation 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 generation 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 one preferred embodiment of the present invention and the present invention is not limited to the following examples.

(Example 1)

After dissolving 1 g of ruthenium chloride and 3 g of ammonium metatangate in 4 ml of water, 1 g of ketjen black was added to the prepared solution and mixed. The prepared mixed solution was first vacuumed at 150 ° C. for 12 hours. The powder obtained after the first vacuum treatment was put into 4 ml of a selenium acid solution having a concentration of 0.0075%, and mixed evenly. Thereafter, the solution obtained in the above process was subjected to secondary vacuum treatment at 150 ° C. for 12 hours in a vacuum state. The powder obtained by the secondary vacuum treatment was heat-treated at 250 ° C. for 3 hours in a hydrogen gas atmosphere to prepare a cathode catalyst for a fuel cell.

(Comparative Example 1)

0.6 g ruthenium carbonyl and 0.6 g tungstencarbonyl were dissolved in 150 ml benzene. 0.01 g of selenium powder and 1 g of ketjen black were added to the prepared solution, stirred for 24 hours while refluxing at 120 ° C., washed, and dried at 80 ° C. for 12 hours. The powder obtained in the above process was heat-treated at a temperature of 250 ° C. for 3 hours in a hydrogen atmosphere to prepare a cathode catalyst for a fuel cell.

In Comparative Example 1, a catalyst in which crystalline Ru-W-Se was supported on Ketjenblack was obtained, and in Example 1, a catalyst in which crystalline and amorphous Ru-W-Se was supported on Ketjenblack was obtained.

3 is a graph showing the results of X-ray diffraction analysis of the catalyst of Example 1. Of the three largest peaks in FIG. 3, a peak at 27 degrees is a peak of carbon, a peak at 30 degrees is a peak of tungsten, and a peak at 45 degrees is a peak of ruthenium. The other broadly distributed small peaks are all ruthenium peaks. There is no peak of selenium.

This shows that the amount of selenium is very small and all particles of selenium are located on the ruthenium-tungsten alloy. The peak of tungsten and the main peak of ruthenium (45 degrees) have the same intensity as the peak of carbon, and since carbon is amorphous, it can be seen that other materials besides carbon are close to amorphous. In addition, there is a wide range of ruthenium peak, which shows that the size of the ruthenium particles is very small. The ruthenium particles are approximately 2.5 to 3.5 nm in size.

4 is a TEM photograph of the catalyst of Example 1. FIG. Figure 4 is a photograph of four different parts of the catalyst of Example 1 to increase the reliability. In FIG. 4, the dark dots represent Ru-W-Se, and the widely distributed gray portions represent portions of amorphous carbon. There is a difference in contrast in the part showing Ru-W-Se. The darker it is, the closer it is to crystalline. This shows that the crystalline Ru-W-Se and the amorphous Ru-W-Se are mixed in the catalyst of Example 1.

To determine the activity of the catalysts of Example 1 and Comparative Example 1, Oxygen gas was bubbling for 2 hours in a sulfuric acid solution of 0.5 M concentration to prepare an oxygen saturated sulfuric acid solution, and the catalyst of Example 1 and the catalyst of Comparative Example 1 were each glassy carbon. 3.78 x 10 ^-3 mg each was loaded as a working electrode, the platinum mesh was placed in the sulfuric acid solution as a counter electrode, and the current density was measured while changing the voltage.

5 is a curve showing the current density according to the voltage change of the catalyst of Example 1 and Comparative Example 1. 5, it was confirmed that the catalyst of Example 1 exhibited much improved activity compared to that of Comparative Example 1.

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 (18)

Carbon-based materials; And Crystalline M ₁ -M ₂ -Ch and amorphous M ₁ -M ₂ -Ch supported on the carbonaceous material (M ₁ is a metal selected from the group consisting of Ru, Pt, and Rh, and M ₂ is composed of W and Mo) And a metal selected from the group, and Ch is a chalcogen element selected from the group consisting of S, Se, and Te). The method of claim 1, The content of the crystalline M ₁ -M ₂ -Ch and amorphous M ₁ -M ₂ -Ch in M ₁ -M ₂ -Ch included in the cathode catalyst is 20 to 80% by weight of crystalline M ₁ -M ₂ -Ch, A cathode catalyst for a fuel cell, wherein the amorphous M ₁ -M ₂ -Ch is 20 to 80% by weight. The method of claim 2, The content of the crystalline M ₁ -M ₂ -Ch and amorphous M ₁ -M ₂ -Ch in the M ₁ -M ₂ -Ch included in the cathode catalyst is 30 to 70% by weight of crystalline M ₁ -M ₂ -Ch, A cathode catalyst for a fuel cell, wherein amorphous M ₁ -M ₂ -Ch is 30 to 70% by weight. The method of claim 3, wherein The content of the crystalline M ₁ -M ₂ -Ch and amorphous M ₁ -M ₂ -Ch in M ₁ -M ₂ -Ch included in the cathode catalyst is 40 to 60% by weight of crystalline M ₁ -M ₂ -Ch, A cathode catalyst for a fuel cell, wherein amorphous M ₁ -M ₂ -Ch is 40 to 60% by weight. The method of claim 1, The ratio of M ₁ to M ₂ of M ₁ -M ₂ -Ch is 1 to 6 to 8 for the cathode catalyst for fuel cells. The method of claim 1, The ratio of M ₁ to Ch of M ₁ -M ₂ -Ch is 1 to 0.5 to 1 cathode for fuel cell. 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, acetylene black, activated carbon, carbon nanotubes, carbon nanofibers and carbon nanowires. 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 anode electrode and the cathode electrode includes a conductive electrode substrate and a catalyst layer formed on the electrode substrate, 8. The membrane-electrode assembly of a fuel cell, wherein the catalyst layer of the cathode comprises the cathode catalyst according to any one of claims 1 to 7. The method of claim 8, 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 9, The polymer resin may be a fluorine polymer, a benzimidazole polymer, a polyimide polymer, a polyetherimide polymer, a polyphenylene sulfide polymer, a polysulfone polymer, a polyether sulfone polymer, a polyether ketone polymer, a 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 10, The polymer resin is tetrafluoroethylene including poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), sulfonic acid group. Copolymers of fluorovinyl ethers containing sulfonic acid groups, defluorinated sulfided polyether ketones, aryl ketones, poly [2,2 '-(m-phenylene) -5,5'-bibenzimidazole] (poly [ 2,2 '-(m-phenylene) -5,5'-bibenzimidazole]) and poly (2,5-benzimidazole). The membrane-electrode assembly for a fuel cell, which is at least one polymer resin selected from the group consisting of: The method of claim 8, The catalyst layer of the anode electrode is platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum-M alloy (M is Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Membrane-electrode assembly for a fuel cell comprising at least one catalyst selected from the group consisting of one or more transition metals selected from the group consisting of Cu and Zn. The method of claim 12, The catalyst included in the catalyst layer of the anode electrode is a carrier selected from the group consisting of graphite, denka black, ketjen black, acetylene black, activated carbon, carbon nanotubes, carbon nanofibers and carbon nanowires, alumina, silica, titania and zirconia Membrane-electrode assembly for fuel cell. The method of claim 8, The catalyst layer further comprises at least one binder selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride, polyvinyl alcohol, cellulose acetate and poly (perfluorosulfonic acid). Membrane-electrode assembly for a fuel cell. The method of claim 8, The electrode substrate may be formed of a carbon film, a carbon cloth, a carbon felt, a carbon felt, and a metal cloth (a porous film composed of a metal in a fibrous state or a metal film formed on a surface of a cloth formed of polymer fibers). Membrane-electrode assembly for a fuel cell comprising at least one conductive substrate selected from the group consisting of. An electricity generating unit including a membrane-electrode assembly according to claim 8 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 16, 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 17, And the fuel cell system is a direct oxidation fuel cell.

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