KR20090104210A - Development of advanced performance in fuel cell with mixture of metal/CNF/ACF and metal/carbon composites - Google Patents

Abstract

PURPOSE: A polymer electrolyte fuel cell through the combination of metal/CNF/ACF catalyst and metal/carbon catalyst is provided to efficiently perform an electrode structure control of a fuel battery and electrode reaction of a CGMRDUS carrier. CONSTITUTION: A metal-complex carbon support for a fuel cell electrode catalyst is the combination of both a metal catalyst supported on carbon nano fibers grown up on activated carbon fibers and a metal catalyst supported on activated carbon. A method for manufacturing the metal-complex carbon support comprises the steps of surface-processing activated carbon fibers; growing carbon nano fiber through pyrolysis by adding a metal precursor to surface-treated activated carbon fiber; impregnating and drying metal in carbon nano fibers grown up on the activated carbon fiber; impregnating and drying metal on the activated carbon fiber; and mixing and plasticizing the product.

Description

Development of advanced performance in fuel cell with mixture of metal / CNF / ACF and metal / carbon composites} through the combination of metal-carbon nanofiber-active carbon fiber catalyst and metal-active carbon catalyst

The present invention optimizes the electrode structure through a combination of a catalyst prepared by growing carbon nanofibers on an activated carbon fiber by pyrolysis and supporting the transition metal precursor using the catalyst, and a catalyst supporting the transition metal precursor on the activated carbon. The present invention relates to the development of control and the electrode performance of fuel cells.

Fuel cell is a power generation device that directly converts chemical energy of fuel into electric energy by electrochemical reaction. It has higher power generation efficiency than other power generation devices such as diesel power generation and steam gas turbine device. This has a small advantage. In detail, the fuel cell supplies a fuel gas containing hydrogen to the anode and an oxidizing gas containing oxygen to the cathode. The fuel cell supplies electrical energy by an electrochemical reaction between hydrogen and oxygen. Since it is an eco-friendly device with no emission of noise and low noise and vibration, many researches are being conducted as a next-generation energy source. Especially, it is developed to be used as a driving energy source for moving bodies such as automobiles because it does not emit exhaust gas. Practical use is in sight. The fuel cells are classified into alkali type, phosphate type, molten carbonate, solid oxide, and polymer fuel cell according to the type of electrolyte used. Among these, a fuel cell for a mobile power source is a polymer electrolyte fuel cell (PEMFC, polymer). The electrolyte membrane fuel cell (DMFC) and direct methanol fuel cell (DMFC) are known to be the most suitable.

Since PEMFC and DMFC use a polymer as an electrolyte, there is no risk of corrosion or evaporation by an electrolyte, and since a high current density can be obtained per unit area, the output characteristics are much higher than those of other fuel cells, and the operating temperature is low. It is a fuel cell.

The unit cells of the PEMFC and DMFC include a Nafion sheet, a platinum / carbon catalyst layer serving as an electrode, a Teflon-treated carbon paper, a separator, and an end plate to a current collector on both sides of a dry layer of a Nafion solution. In the stacked structure, hydrogen gas, a fuel gas supplied through a gas flow channel, reacts with a platinum / carbon catalyst constituting an anode to desorb electrons to become hydrogen ions, and the NaFion sheet is a polymer electrolyte membrane. And Nafion solution is passed through the drying layer to the negative electrode of the opposite side. Oxygen ions reduced by the electrons moved through the external gas flow channel to the cathode through an external circuit react with the hydrogen ions moved to the cathode to generate water at the cathode surface. Is discharged to the outlet of the gas flow channel with excess oxygen gas which has not reacted.

 In this case, electrons generated by the catalytic reaction flow along an external circuit to generate electricity.

In general, a catalyst in which platinum or platinum-based alloys are supported on amorphous carbon is widely used as an electrode material for fuel cells. However, such an electrode material has a disadvantage in that the crystal size of the metal increases as the amount of the supported metal increases. On the other hand, as a method to improve the utilization of precious metals such as platinum, the platinum supported thereon has a higher specific surface area when carbon having a higher specific surface area is produced and then loaded with platinum. It has a much smaller crystal size than the vulcan XC carbon. However, such high surface area carbons, carbon nanotubes (CNTs), carbon nanofibers (CNFs), etc., can be loaded in a conventional manner according to the amount required by PEMFC and DMFC (20-60%). none. Therefore, there are methods of supporting the surface using a method of oxidizing using a strong acid or a strong base. However, this method has a disadvantage in that the surface transfer characteristics of hydrogen cations are significantly lowered by the micropores when preparing the catalyst.

 The present invention was devised to solve the limitations of activated carbon, carbon nanotubes, carbon nanofibers, etc. used as a conventional support, and carbon nanofibers grown on activated carbon fibers and transition metal catalysts Maximizes catalyst performance by mixing the transition metal catalysts supported in a proper combination to have electrical conductivity and reaction area to control the electrode structure of the fuel cell and the three-phase structure for efficient propagation of electrode reaction of the CGMRDUS carrier. The purpose is.

In the present invention, the metal-composite carbon support may not only chemically bond various metals to carbon, but also introduce two or more metal precursors including platinum to prepare a composite to obtain an alloy or metal mixture having a wide variety of properties. do. The present invention relates to a method for producing an alloy-carbon composite support or a metal mixture-carbon composite support that reduces the amount of platinum and increases the electrocatalyst activity of a fuel cell.

    The metal-composite carbon support of the present invention can be usefully used as an electrode of a fuel cell. It can be seen in the examples described later that the metal-composite carbon support of the present invention exhibits excellent catalytic activity in the electrode reaction of the fuel cell.

The metal-composite carbon support of the present invention may be used as an electrode catalyst of any fuel cell using hydrogen or hydrocarbon as a fuel, but in particular, a catalyst of a polymer electrolyte fuel cell (PEMFC) and a direct methanol fuel cell (Direct methanol Feul Cell) Useful as

The present invention provides a low temperature fuel cell by controlling and creating a fuel cell electrode metal-carbon composite structure through an optimal combination of a metal catalyst supported on carbon nanofibers grown on activated carbon fibers and a metal catalyst supported on activated carbon. It relates to electrode production.

The present invention also provides a method for producing the metal-carbon composite, which is composed of the following steps.

(a) surface treatment of activated carbon fibers

(b) growth of carbon nanofibers through pyrolysis of hydrocarbons by adding metal precursors to the surface-treated activated carbon fibers;

(c) impregnating and drying the metal in the carbon nanofibers grown on the activated carbon fibers prepared in the step;

(d) impregnating and drying the metal on the activated carbon;

(e) mixing and firing the resultant product.

The metal constituted for the combination of the metal catalyst supported on the carbon nanofibers grown on the activated carbon fiber and the metal catalyst supported on the activated carbon is not particularly limited. For example, Pt, Ru, Cu, Ni, Mn, Co , W, Fe, Ir, Rh, Ag, Au, Os, Cr, Mo V, Pd, Ti, Zr, Zn, B, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Mg, Sr, Ce, Pr, Nd, Sm, Re or combinations thereof may be used, and precursors of these metals include (NH 3) 4 Pt (NO 3) 2, H 2 PtCl 6-x H 20, (NH 3) 6 RuCl 3, Ni (NO 3) 2, MnCl 2, CoCl 2, (NH 4) 6 W 12 O 39, FeCl 2, (NH 4) 3 IrCl 6, (NH 4) 3 RhCl 6, AgCl and the like can be used.

At this time, the metal impregnated in the carbon nanofibers grown on the activated carbon fiber may be included in one metal alone, or may include two or more metals. When two or more metals are included, the reaction conditions may be adjusted to impregnate the alloy, or may be impregnated separately in a mixed form. In addition, the impregnation rate of the metal can also be adjusted in various ways. For example, platinum or ruthenium may be impregnated separately using (NH3) 4Pt (NO3) 2 and (NH3) 6RuCl3 as precursors of platinum and ruthenium, or may be impregnated in the form of platinum and ruthenium alloys.

Meanwhile, as described above, the metals listed above may be impregnated alone, or two or more composite components may be impregnated, but in the case of the composite components, platinum is preferably included together.

The step (a) is a surface treatment step of the activated carbon fiber, it is preferable to use hydrochloric acid and high purity nitric acid as the surface treatment agent.

It is also possible to use strong salts such as KOH (potassium hydroxide) instead of using high purity acids.

The step (b) is a step for growing carbon nanofibers on the surface-treated activated carbon fibers, preferably using nickel nitrate tetrahydrate dissolved in acetone as a carbon precursor, and methane at a temperature of 500 to 550 ° C. It is preferably carried out in an atmosphere.

The step (e) is a step of combining the metal-carbon nanofiber-activated carbon fiber and the metal-activated carbon obtained through the above step, a process of obtaining a new composite.

The step (e) is preferably carried out in a hydrogen atmosphere of 350-900oC.

In the metal-carbon composite prepared by the above process, 1 to 95% by weight of metal and 5-99% by weight of carbon are contained, preferably 4 to 60% by weight, of the metal-carbon composite. 40 to 96% by weight of carbon is included.

On the other hand, when the metal used for the metal-carbon composite of the present invention comprises platinum as the first component and other metals as the second component, the second metal component is Ru, Cu, Ni, Mn, Co, W , Fe, Ir, Rh, Ag, Au, Os, Cr, Mo, V, Pd, Ti, Zr, Zn, B, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Mg, Sr , Ce, Pr, Nd, Sm, Re or a mixed component thereof may be used. As in the present invention, a metal catalyst supported on carbon nanofibers grown on activated carbon fibers and a metal catalyst supported on activated carbon fibers may be used. The combination is preferably a combination of 1: 9 to 5: 5. When the two catalysts are combined in the above ratio, it can be seen that the characteristics of the fuel cell are more excellent. This is an important element of the present invention as the three-phase configuration in which the hydrogen ion conduction characteristics and the electrical conductivity are improved by the optimization of the electrode structure is realized. In addition, when two kinds of carbon supports are simultaneously introduced and heat treated as in the present invention, metal and carbon may chemically form covalent bonds, thereby inducing active progression of spillover of adsorbed hydrogen. That is, it is very important to increase the electrode reaction rate of the fuel cell by realizing the electrode structure that combines the hydrogen-absorbing medium characteristics, so that the activity of the metal catalyst maintained in high dispersion has the electrode activity with low resistance even at high current. can do. That is, when the two carbon supports of the present invention are introduced and used at the same time, the electrode configuration can be optimized and the electrode reaction speed of the fuel cell can be improved.

Example 1

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

First, 1 g of activated carbon fibers were finely ground and put into 200 mL of 0.2 M hydrochloric acid solution and stirred at room temperature. After stirring, the mixture was filtered with washing with distilled water. The powder obtained after drying is added to 200 mL of 6M nitric acid solution and stirred at 80 ° C. After stirring was filtered while washing with distilled water. Based on 1 g of the pretreated activated carbon fiber obtained according to the above method, add 0.2 M of nickel nitrate tetrahydrate dissolved in acetone, and then stir. This was dried at a temperature of 40 C using a vacuum dryer to allow the Ni precursor solution to merge. Then put into a reactor and pyrolyzed under methane (NH4) for 1 hour under 530 C. This is a process for growing carbon fibers on activated carbon fibers.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

Pt precursor solution is added and stirred so that 20wt% Pt is added on the basis of 1g of carbon nanofibers grown on activated carbon fibers prepared according to the method of A. H 2 PtCl 6 was used as the precursor. Activated carbon also impregnates Pt in this manner. As a reducing agent, NaBH4 was used for the dropping process. Thereafter, heat treatment was performed in a 350 degree hydrogen atmosphere.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

The platinum-compound carbon support of the present invention was prepared by combining the catalysts prepared according to the above methods A and B. The combination ratio is 30 wt% carbon nanofibers and 70 wt% activated carbon fibers grown on activated carbon fibers based on the composite carbon support.

Example 2

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 20 wt% of carbon nanofibers and 80 wt% of activated carbon fibers grown on activated carbon fibers based on the composite carbon support. It was.

Example 3

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1, except that the combination ratio was 10 wt% of carbon nanofibers grown on activated carbon fibers and 90 wt% of activated carbon fibers based on the composite carbon support. It was.

Example 4

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 0 wt% of carbon nanofibers grown on activated carbon fibers and 100 wt% of activated carbon fibers based on the composite carbon support. It was.

Example 5

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 40 wt% of carbon nanofibers and 60 wt% of activated carbon fibers grown on activated carbon fibers based on the composite carbon support. It was.

Example 6

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 50 wt% of carbon nanofibers and 50 wt% of activated carbon fibers grown on activated carbon fibers based on the composite carbon support. It was.

Example 7

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 60 wt% of carbon nanofibers and 40 wt% of activated carbon fibers grown on activated carbon fibers based on the composite carbon support. It was.

Example 8

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 70 wt% of carbon nanofibers and 30 wt% of activated carbon fibers grown on activated carbon fibers based on the composite carbon support. It was.

Example 9

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 80 wt% of carbon nanofibers and 20 wt% of activated carbon fibers grown on activated carbon fibers based on the composite carbon support. It was.

Example 10

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 90 wt% of carbon nanofibers and 10 wt% of activated carbon fibers grown on activated carbon fibers based on the composite carbon support. It was.

Example 11

A. Preparation of Carbon Nanofibers Grown on Activated Carbon Fibers

Carbon nanofibers grown on activated carbon fibers were prepared in the same manner as in Example 1.

B. Preparation of Platinum Catalyst Supported on Carbon Nanofibers Grown on Activated Carbon Fiber

The platinum catalyst supported on carbon nanofibers grown on activated carbon fibers was prepared in the same manner as in Example 1.

C. Combination of carbon nanofibers grown on activated carbon fiber and platinum catalyst supported on activated carbon

 The metal-composite carbon support of the present invention was prepared in the same manner as in Example 1 except that the combination ratio was 100 wt% of carbon nanofibers and 0 wt% of activated carbon fibers grown on activated carbon fibers based on the composite carbon support. Was

Experimental Example 1. Structural analysis

In order to analyze the structure of the carbon nanofibers grown on the activated carbon prepared in the above embodiment, a transmission electron microscope (TEM), an X-ray diffractometer (XRD), a pore analyzer ) Was used.

1 is a result of observing the carbon nanofibers grown on the activated carbon fiber prepared according to Example 1 by SEM and as can be seen from the carbon nanofibers grown on the activated carbon fiber according to the present invention has a three-dimensional structure Was observed.

Figure 2 is the result of observing the powder of the platinum-composite carbon support impregnated in carbon nanofibers grown on the activated carbon fiber prepared according to Example 2 by TEM and the platinum-composite carbon according to the present invention The support was observed in a three-dimensional structure.

3 is an XRD analysis result of the platinum-composite carbon support prepared according to Example 2 of the present invention, and it can be seen that carbon nanofibers grown on activated carbon fibers having nanostructures according to the present invention are shown.

FIG. 4 is a result of observing the pore structure of a combination of a platinum catalyst supported on carbon nanofibers grown on activated carbon prepared on Example 3 and a platinum catalyst grown on activated carbon.

From these results, the platinum-carbon catalyst prepared by the conventional method has a simple RDu of metal and carbon, but the platinum-composite carbon support prepared according to the present invention clearly shows that platinum is a new composite chemically formed with carbon. Can be. Thus, the metal is in a chemical bond with the very stable ring carbon is a result of the characteristic combination of the present invention.

As can be seen from FIG. 2, the combination of the platinum-composite carbon support prepared according to the present invention showed that platinum was polydispersed on the carbon of two-dimensional or three-dimensional structure rolls.

Electrochemical and electrode-electrolyte conjugate performance verification experiments were performed to evaluate the activity as a catalyst of a fuel cell using the combination of platinum-composite carbon supports prepared in Examples 1 to 12.

Experimental Example 1. Performance test of electrode electrolyte assembly

The catalyst prepared in Example 1 of the present invention was prepared as an anode of a polymer electrolyte membrane fuel cell (PEMFC), and a commercial Pt / C (E-TEK) catalyst was prepared as a cathode to a Nafion electrolyte membrane (Nafion 112). Electrolyte-electrode assembly (MEA) was prepared by direct spraying. 15% of a Nafion electrolyte solution was added to the catalytic coating layer of the anode. A commercial gas diffusion layer was used as the gas diffusion layer (GDL). The two oxidation / reduction electrodes were pressed for 1 minute with the Nafion electrolyte membrane interposed therebetween to prepare an assembly, and the performance results of each combination are shown in FIGS. 5 and 6. At this time, the conditions of the anode is 0.4mg Pt / sq.cm, hydrogen 150ml / min The conditions of the cathode are 0.4mg Pt / sq.cm, oxygen 200ml / min or air 200ml / min. Fig. 6 is a performance result when the pressure of the fuel cell rear valve is 1 bar under the above conditions.

Comparative Experiment 1

As the anode catalyst, the experiment was carried out under the same conditions and procedures as those of Experimental Example 1, except that commercial 20 wt% Pt / C (E-TEK) was used instead of the platinum-composite carbon support of the present invention. The results are shown in FIGS. 5 and 6.

As can be seen from the performance results of FIGS. 5 and 6, the electrode electrolyte assembly using the platinum-composite carbon support according to the present invention showed excellent performance and high open circuit voltage at all reaction temperatures. In particular, the effect is excellent when the cathode material is air and the pressure of the rear valve is 1 bar.

As described above, the combination of the metal-composite carbon support according to the present invention has the effect of further improving the performance of the fuel cell. This makes it possible to use it in the fuel cell field that generates electricity using hydrogen and hydrocarbons, which are clean energy, and as an alternative to alternative energy due to the depletion of fossil fuel, which is currently being actively researched, and also depletion of existing energy resources and We can solve the pollution problem drastically.

1 is a SEM observation result of carbon nanofibers grown on activated carbon fibers prepared according to Example 1 of the present invention.

2 is a TEM observation result of a metal-carbon composite impregnated with carbon nanofibers grown on activated carbon fibers prepared according to Example 3 of the present invention.

3 is an XRD observation result of a metal-carbon composite impregnated with carbon nanofibers grown on activated carbon fibers prepared according to Example 3 of the present invention.

FIG. 4 shows the results of the polymer electrolyte fuel cell performance comparison of the electrode-electrolyte assembly using the platinum-composite carbon support prepared according to Example 3 of the present invention and a commercial fuel cell catalyst. Pressurized), 2 when using platinum-composite carbon support (no trailing valve pressurized), 3 when using commercial platinum catalyst (pressing backside valve), 4 when using commercial platinum catalyst (no trailing valve pressurized)

5 is a conceptual diagram of a platinum-composite carbon support prepared according to Example 3 of the present invention;

1 is supported platinum, 2 is carbon nanofibers grown on activated carbon fibers, 3 is activated carbon, 4 is Nafion 5 is activated carbon.

Claims (9)

Metal-composite carbon support for fuel cell electrode catalysts characterized by a combination of a metal catalyst supported on carbon nanofibers grown on activated carbon fibers and a metal catalyst supported on activated carbon The method of claim 1 The metal is Pt, Ru, Cu, Ni, Mn, Co, W, Fe, Ir, Rh, Ag, Au, Os, Cr, Mo Group consisting of V, Pd, Ti, Zr, Zn, B, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Zb, Mg, Sr, Ce, Pr, Nd, Sm, Re and mixtures thereof Combination of metal-composite carbon support for fuel cell electrocatalyst, characterized in that selected from The method of claim 1 The metal is included in the amount of 1 to 95% by weight based on the weight of the metal-composite carbon support, the carbon is fuel cell electrode characterized in that it comprises an amount of 5 to 99% by weight of the metal-carbon composite catalyst The method of claim 3 The one metal is contained in the amount of 4 to 60% by weight relative to the weight of the metal-composite carbon support, the carbon is a fuel cell electrode catalyst characterized in that it comprises an amount of 40-96% by weight The fuel cell according to claim 1, wherein the catalyst of claim 1 employs an electrode coated on an electrolyte membrane, a gas diffusion layer, and an electrode coated by a decal method as a membrane-electrode assembly (MEA). The method of claim 5, The fuel cell is a low-temperature fuel cell (<200oC), characterized in that using hydrogen or hydrocarbon as fuel. (a) surface treatment of activated carbon fibers (b) adding carbon precursors to the surface-treated activated carbon fibers to grow carbon nanofibers through pyrolysis; (c) impregnating and drying the metal in the carbon nanofibers grown on the activated carbon fibers prepared in the step; (d) impregnating and drying the metal on the activated carbon; (e) a method for producing a metal-composite carbon support for an electrode catalyst prepared by mixing and firing the resultant The method of claim 8 The metal-composite carbon support is a method for producing a combination and firing of a metal catalyst supported on carbon nanofibers grown on activated carbon fibers and a metal catalyst supported on activated carbon The method of claim 8 The step (b) is carried out at a temperature of 500 ~ 550oC, the step (e) is a manufacturing method of a metal-composite carbon support for fuel cell electrode catalyst, characterized in that carried out at a temperature of 350 ~ 900oC.

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