KR100759431B1 - Cathode catalyst for fuel cell, method for preparing the same, membrane-electrode assembly for fuel cell comprising the same, and fuel cell system comprising the same - Google Patents

Abstract

A cathode catalyst, a method for preparing the same, and a membrane-electrode assembly and a fuel cell system including the same are provided to improve an oxygen reduction reactivity and a catalytic efficiency. A cathode catalyst comprises a cluster compound which includes an iron-salen complex compound and a Me-salen complex compound, and in which a central metal of the iron-salen complex compound is bound to a central metal of the Me-salen complex compound. The cluster compound is preferably represented by the formula 1, wherein Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni and a combination thereof, and R1 to R28 are the same or are independently H or an alkyl. The cathode catalyst is prepared by a method comprising the steps of: mixing a salen derivative, a Fe-containing precursor, a Me-containing precursor and a solvent; and reacting the resulting mixture to produce a cluster compound in which a central metal of the iron-salen complex compound is bound to a central metal of the Me-salen complex compound.

Description

Cathode catalyst for fuel cell, method for manufacturing the same, membrane-electrode assembly for fuel cell comprising the same, and fuel cell system including the same AND FUEL CELL SYSTEM COMPRISING THE 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 is a view schematically showing the structure of a fuel cell system according to an embodiment 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. More particularly, a cathode catalyst for a fuel cell having excellent catalyst efficiency, a method for manufacturing the same, Membrane-electrode assembly for a fuel cell comprising the same, and a fuel cell system comprising the same.

[Prior art]

A fuel cell is a power generation system that directly converts the chemical reaction energy of hydrogen and oxygen contained in hydrocarbon-based materials such as methanol, ethanol and natural gas into electrical energy.

Such a fuel cell is a clean energy source that can replace fossil energy, and has a merit of outputting a wide range of outputs by stacking unit cells, and having an energy density of 4 to 10 times compared to 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).

The polymer electrolyte fuel cell has an advantage of having a high energy density and a high output, but requires attention to handling hydrogen gas and reforms fuel for reforming methane, methanol, natural gas, etc. to produce hydrogen as fuel gas. There is a problem that requires additional equipment such as a device.

On the other hand, the direct oxidation fuel cell has a lower energy density than the polymer electrolyte fuel cell, but it is easy to handle fuel and has a low operating temperature, so that it can be operated at room temperature, in particular, it does not require a fuel reformer.

In such fuel cell systems, the stack that substantially generates electricity comprises several unit cells consisting of a membrane-electrode assembly (MEA) and a separator (also called a bipolar plate). It has a structure laminated to several tens. The membrane-electrode assembly has a structure in which an anode electrode and a cathode electrode are positioned with a polymer electrolyte membrane including a hydrogen ion conductive polymer interposed therebetween.

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.

An object of the present invention is to provide a cathode catalyst for a fuel cell which is excellent in catalyst efficiency.

Another object of the present invention is to provide a production 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.

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

In order to achieve the above object, the present invention includes an iron-salen complex and Me-salen complex (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof), Provided is a cathode catalyst for a fuel cell comprising a cluster compound in which the center metal of the -salen complex and the center metal of the Me-salen complex are combined.

The cluster compound is preferably represented by the following formula (1).

[Formula 1]

(Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof, and R ₁ to R ₂₈ are the same or each independently H, or alkyl)

The cathode catalyst for fuel cell of the present invention may comprise a polymer of a cluster compound.

The present invention also provides a mixture of a salen derivative, a Fe-containing precursor, a Me-containing precursor (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof), and a solvent, Reacting to produce a cluster compound in which the center metal of the iron-salen complex and the center metal of the Me-salen complex (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, and Ni) are combined. A method for producing a battery cathode catalyst is provided.

The present invention also provides an anode electrode and a cathode electrode positioned opposite each other; And a polymer electrolyte membrane positioned between the anode electrode and the cathode electrode, wherein the cathode electrode includes the cathode catalyst.

The present invention also provides a fuel cell system including an electric generator, a fuel supply unit and an oxidant supply unit including a membrane-electrode assembly including the cathode catalyst.

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

The present invention includes iron-salen complexes and Me-salen complexes (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof), and the center metal and Me of the iron-salen complexes Provided is a cathode catalyst for a fuel cell comprising a cluster compound in which the central metal of the salen complex is bonded.

In fuel cells, oxidants, hydrogen ions, and electrons react on the catalyst of the cathode electrode to generate water while producing water. Since oxygen is mainly used as the oxidant, the cathode catalyst for a fuel cell should be a material capable of adsorbing oxygen well and facilitating the reaction with hydrogen. That is, strong oxygen reduction reactivity is required. In general, compounds containing iron-nitrogen bonds (FeN ₂ ) and compounds containing metal-oxygen bonds (MeO ₂ ) are known to have strong oxygen reduction reactivity. The cathode catalyst for a fuel cell of the present invention includes both the iron-nitrogen bond (FeN ₂ ) and the metal-oxygen bond (Me-0), and thus has a strong oxygen reduction reactivity.

The cluster compound is preferably represented by the following formula (1).

[Formula 1]

(Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof, and R ₁ to R ₂₈ are the same or each independently H, or alkyl)

R ₁ to R ₂₈ are the same or each independently H, or alkyl is preferred. The alkyl is preferably C ₁ to C ₆ alkyl, more preferably CH ₃ , C ₂ H ₅ , or C ₃ H ₇ .

The iron-salen complex and Me-salen complex may have a planar shape. When the iron-salen complex and the Me-salen complex have a planar shape, the iron-salen complex and the Me-salen complex may be present on different planes.

It is preferable that Me is Co. This is because when Me is Co, the cluster compound has a Co—O bond and thus a strong oxygen reduction reactivity.

The fuel cell cathode catalyst may comprise a polymer of a cluster compound.

The polymer of the cluster compound can be produced by electropolymerizing the cluster compound.

The mechanism of the electropolymerization is assumed to be similar to the polymerization mechanism of the conjugated polymer (conjugated polymer) as follows.

M ^- e - → CR

2CR → D + 2H ⁺

Here, M means a monomer, CR means a cation radical, and D means a dimer.

Since the electropolymerization method of the cluster compound may be prepared by a method well known in the art, detailed description thereof will be omitted. However, when describing the electropolymerization method of the cluster compound according to an embodiment of the present invention, acetonitrile or dichloromethane as a solvent, if a current density of 6 to 20mC / cm ² is added, ITO (indium tin oxide) electrode or The polymer of the cluster compound may be prepared in the form of a film on the surface of the platinum electrode.

In the polymer of the cluster compound, the ratio of Fe to Me is 15 to 75 atomic% of Fe, and Me (Me is one or more elements selected from the group consisting of Co, Cr, Mn, Mo, and Ni) of 25 to 85 atomic% Is preferably. When the polymer of the cluster compound includes Fe and Me within the above range, it contains iron-nitrogen bond (FeN ₂ ) and metal-oxygen bond (Me-0) in an appropriate ratio, thereby reducing the oxygen of the cathode catalyst for fuel cell May increase reactivity.

The cathode catalyst for a fuel cell may be a mixture of a salen derivative, a Fe-containing precursor, a Me-containing precursor (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof), and a solvent, followed by reaction. It can manufacture.

The salen derivative is preferably represented by the following formula (2).

[Formula 2]

(R ₁ to R ₁₄ are the same or each independently H, or alkyl)

The Fe-containing precursor is preferably selected from the group consisting of Fe nitrate, Fe chloride, Fe acetylacetonate, and combinations thereof, and the Me-containing precursor is Me nitrate, Me chloride, Me acetylacetonate, and these It is preferably selected from the group consisting of

In addition, the solvent is preferably selected from the group consisting of methanol, ethanol, benzene, and combinations thereof.

It is preferable to perform the said reaction at 50-100 degreeC. If the temperature of the reaction is less than 50 ℃, or more than 100 ℃, it is not preferable because it takes a long time to produce the iron-salen complex or Me-salen complex.

The present invention also provides an anode electrode and a cathode electrode positioned opposite each other; And a polymer electrolyte membrane positioned between the anode electrode and the cathode electrode, wherein the cathode electrode includes the cathode catalyst of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

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 anode layer of the catalyst layer 33, the oxidation reaction of the fuel occurs, and includes a catalyst for promoting the reaction. Participating in the reaction of the fuel cell, anything that can be used as a catalyst can be used, and a representative example thereof is platinum-based Catalysts can 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, Zn, Sn, Mo, W, Rh, Ru, and mixtures thereof.

As described above, the anode electrode and the cathode electrode may use the same material, but in order to prevent the catalyst poisoning caused by CO generated during the anode electrode reaction in the direct oxidation fuel cell, a platinum-ruthenium alloy catalyst is used as the anode. It is more preferable as an electrode catalyst. Specific examples include Pt, Pt / Ru, Pt / W, Pt / Ni, Pt / Sn, Pt / Mo, Pt / Pd, Pt / Fe, Pt / Cr, Pt / Co, Pt / Ru / W, Pt / Ru At least one selected from the group consisting of / Mo, Pt / Ru / V, Pt / Fe / Co, Pt / Ru / Rh / Ni, Pt / Ru / Sn / W and mixtures thereof may be used.

The catalyst may be used as the catalyst itself (black), or may be supported on a carrier. As the carrier, carbon-based materials such as graphite, denka black, ketjen black, acetylene black, carbon nanotube, carbon nanofiber, carbon nanowire, carbon nanoball, or activated carbon may be used, or alumina, silica, titania Inorganic fine particles such as zirconia and the like may be used, but carbon-based materials are generally used.

Catalyst layers 33 and 53 of the anode electrode and the cathode electrode may include a binder, it is preferable to use a polymer resin having hydrogen ion conductivity as the binder, more preferably sulfonic acid groups, carboxyl in the side chain Any polymer resin having a cation exchange group selected from the group consisting of an acid group, a phosphoric acid group, a phosphonic acid group and derivatives thereof can be used.

Preferably, 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 polyether And at least one hydrogen ion conductive polymer selected from the group consisting of ether ketone polymers, polyphenylquinoxaline polymers, and mixtures thereof.

More preferably poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ether 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), poly (2,5- Benzimidazole), and mixtures containing at least one hydrogen ion conductive polymer selected from the group consisting of these can be used.

The binder may be used in the form of a single substance or a mixture, and may also be optionally used with a nonconductive polymer for the purpose of further improving adhesion to the polymer electrolyte membrane. It is preferable to adjust the usage-amount so that it may be suitable for a purpose of use.

Examples of the nonconductive polymer include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro alkylvinyl ether copolymer (PFA), and ethylene / tetrafluoro Ethylene / tetrafluoroethylene (ETFE), ethylenechlorotrifluoro-ethylene copolymer (ECTFE), polyvinylidene fluoride, copolymer of polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), dode It is more preferable that it is at least one selected from the group consisting of silbenzenesulfonic acid, sorbitol, and mixtures thereof.

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)) 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. Examples of the fluorine-based resin include polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride alkoxy vinyl ether, and fluorinated ethylene propylene ( Fluorinated ethylene propylene), polychlorotrifluoroethylene or copolymers thereof can 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, and a solvent on the electrode substrate. The binder may be polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride, alkoxy vinyl ether, polyvinyl alcohol, cellulose acetate or These copolymers etc. can be used preferably.

As the solvent, alcohols such as ethanol, isopropyl alcohol, n-propyl alcohol, butyl alcohol, water, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc. may 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 At least one selected from the group consisting of a polymer, a polyether-etherketone-based polymer, a polyphenylquinoxaline-based polymer, and a mixture thereof, and more preferably poly (perfluorosulfonic acid), poly (purple) Fluorocarboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ether containing sulfonic acid groups, defluorinated sulfide polyether ketones, aryl ketones, poly (2,2'-m-phenylene) -5, At least one selected from the group consisting of 5'-bibenzimidazole (poly (2,2 '-(m-phenylene) -5,5'-bibenzimidazole), poly (2,5-benzimidazole) and mixtures thereof One It can be given.

In the hydrogen ion conductive group of the hydrogen ion conductive polymer, H may be substituted with Na, K, Li, Cs or tetrabutylammonium. In the hydrogen ion conductive group of the hydrogen ion conductive polymer, NaOH is substituted when H is replaced with Na, and tetrabutylammonium hydroxide is used when the substituent is substituted with tetrabutylammonium. 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 includes an electricity generation unit including the membrane-electrode assembly for a fuel cell of the present invention, and a separator; A fuel supply unit supplying fuel to the electricity generation unit; And an oxidant supply unit supplying an oxidant to the electricity generation unit.

The electricity generating unit includes a membrane-electrode assembly and a separator (bipolar plate). 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.

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) for supplying fuel and an oxidant to both sides of the membrane-electrode assembly 131 ( 133,135).

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.

(Production of Cathode Catalyst for Fuel Cell)

(Example 1)

1 g of a salen ligand (R ₁ to R ₁₄ in Formula 2 each have a structure of H), 1 g of iron acetylacetonate, 1 g of cobalt acetylacetonate, and benzene (15 ml) as a solvent are mixed, and this mixture is mixed. The reaction product was reacted at 90 ° C. for 3 hours, and the obtained reaction product was dried at 90 ° C. for 24 hours to prepare a cathode catalyst for a fuel cell.

The prepared cathode catalyst has a structure in which each of R ₁ to R ₂₈ in Formula 1 is H, and includes a cluster compound in which a center metal of an iron-salen complex and a center metal of a cobalt-salen complex are bonded. In addition, the iron-salen complex and the cobalt-salen complex had a planar shape, and the iron-salen complex and the Me-salen complex were present on different planes.

(Example 2)

A cathode catalyst for a fuel cell was prepared in the same manner as in Example 1 except that chromium acetylacetonate was used instead of cobalt acetylacetonate.

(Example 3)

A cathode catalyst for a fuel cell was prepared in the same manner as in Example 1 except that manganese acetylacetonate was used instead of cobalt acetylacetonate.

(Example 4)

A cathode catalyst for a fuel cell was prepared in the same manner as in Example 1 except that molybdenum acetylacetonate was used instead of cobalt acetylacetonate.

(Example 5)

A cathode catalyst for a fuel cell was prepared in the same manner as in Example 1 except that nickel acetylacetonate was used instead of cobalt acetylacetonate.

(Comparative Example 1)

Pt / C having 20 wt% of Pt supported on carbon black was used as a cathode catalyst for fuel cells.

(Comparative Example 2)

Co ₃ O ₄ was used as the cathode catalyst for the fuel cell.

(Comparative Example 3)

FeN ₂ was used as a cathode catalyst for fuel cells.

(Performance Measurement of Prepared Cathode Catalysts)

Oxygen gas was bubbled in a 0.5 M sulfuric acid solution for 2 hours to prepare an oxygen saturated sulfuric acid solution, and a catalyst prepared according to Examples 1 to 5 and Comparative Examples 1 to 3 was prepared. 3.78 × 10 ⁻³ mg was loaded onto glassy carbon as a working electrode, and a platinum mesh was placed in the sulfuric acid solution as a counter electrode to measure current density at a voltage of 0.7V. Among these, the results for the cathode catalyst prepared in Example 1, and Comparative Examples 1 to 3 are shown in Table 1 below.

Current density (mA / cm ² ) Comparative Example 1 1.7 Comparative Example 2 0.41 Comparative Example 3 1.4 Example 1 1.75

Referring to Table 1, it can be seen that the cathode catalyst prepared in Example 1 is superior in current density than the cathode catalysts of Comparative Examples 1 to 3. This is because the cathode catalyst prepared in Example 1 includes both an iron-nitrogen (FeN ₂ ) bond and a metal-oxygen (MeO ₂ ) bond, thereby improving the oxygen reduction reactivity of the cathode catalyst. In addition, the cathode catalysts prepared in Examples 2 to 5 exhibited a current density similar to that of the cathode catalysts prepared in Example 1.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

The cathode catalyst for a fuel cell of the present invention includes both an iron-nitrogen (FeN ₂ ) bond and a metal-oxygen (MeO ₂ ) bond, thereby improving the oxygen reduction reactivity of the cathode catalyst and providing a high efficiency catalyst.

Claims (16)

Iron-salen complexes; And Me-salen complex (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof), A cathode catalyst for a fuel cell comprising a cluster compound in which the center metal of the iron-salen complex and the center metal of the Me-salen complex are combined. The method of claim 1, The cluster compound is a cathode catalyst for a fuel cell that is represented by the formula (1). [Formula 1]

(Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof, and R ₁ to R ₂₈ are the same or each independently H, or alkyl) The method of claim 2, Wherein the iron-salen complex and Me-salen complex is a cathode catalyst for a fuel cell having a planar shape. The method of claim 3, Wherein the iron-salen complex and Me-salen complex is a cathode catalyst for a fuel cell that is present on different planes. The method of claim 1, Wherein Me is Co cathode catalyst for fuel cells. The method of claim 1, Cathode catalyst for a fuel cell comprising a polymer of the cluster compound. The method of claim 6, The polymer of the cluster compound is a cathode catalyst for a fuel cell is produced by electropolymerizing the cluster compound. The method of claim 6, The polymer of the cluster compound is 15 to 75 atomic% Fe based on the entire polymer, Me (Me is at least one element selected from the group consisting of Co, Cr, Mn, Mo and Ni) 25 to 85 atomic% Cathode catalyst for a fuel cell comprising a. Mixing a salen derivative, a Fe-containing precursor, a Me-containing precursor (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof), and a solvent; And Reacting the mixture to prepare a cluster compound in which the center metal of the iron-salen complex and the center metal of the Me-salen complex (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, and Ni) are combined; Method for producing a cathode catalyst for a fuel cell comprising a. The method of claim 9, The salen derivative is a method for producing a cathode catalyst for a fuel cell is represented by the following formula (2). [Formula 2]

(R ₁ to R ₁₄ are the same or each independently H, or alkyl) The method of claim 9, And said Fe-containing precursor is selected from the group consisting of Fe nitrate, Fe chloride, Fe acetylacetonate, and combinations thereof. The method of claim 9, The Me-containing precursor (Me is an element selected from the group consisting of Co, Cr, Mn, Mo, Ni, and combinations thereof) is a group consisting of Me nitrate, Me chloride, Me acetylacetonate, and combinations thereof Method for producing a cathode catalyst for a fuel cell is selected from. The method of claim 9, The solvent is a method for producing a cathode catalyst for a fuel cell is selected from the group consisting of methanol, ethanol, benzene, and combinations thereof. The method of claim 9, The reaction is a method for producing a cathode catalyst for fuel cells that is carried out at 50 to 100 ℃. An anode electrode and a cathode electrode located opposite each other; And An electrolyte located between the anode electrode and the cathode electrode; 9. The membrane-electrode assembly of a fuel cell, wherein said cathode electrode comprises the cathode catalyst of any one of claims 1-8. An electricity generating unit including an electrode electrode and a separator including an anode electrode and a cathode electrode positioned opposite to each other, and an electrolyte positioned between the anode electrode and the cathode electrode; A fuel supply unit supplying fuel to the electricity generation unit; And An oxidant supply unit for supplying an oxidant to the electricity generation unit, 10. The fuel cell system of claim 1, wherein the cathode comprises the cathode catalyst of any one of claims 1-8.

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