KR20240081263A - Oxidation resistant catalyst for fuel cell, manufacturing method thereof and fuel cell comprising the same - Google Patents

Abstract

The present invention relates to an oxidation-resistant catalyst for fuel cells, a method of manufacturing the same, and a fuel cell containing the same. The fuel cell catalyst according to the present invention has the characteristic of oxidation resistance of metal oxide while maintaining the electrical conductivity of the carbon support. Accordingly, the catalytic activity of platinum particles, which are the active point of the fuel cell, can be improved, and the metal oxide prevents the platinum particles from directly interacting with the carbon support, which has the advantage of solving the carbon corrosion problem that occurs at the platinum/carbon interface. There is.

Description

Oxidation resistant catalyst for fuel cell, manufacturing method the same and fuel cell comprising the same}

The present invention relates to an oxidation-resistant catalyst, and more specifically, to a catalyst support suitable for fuel cell applications, an oxidation-resistant fuel cell catalyst with excellent electrical conductivity of the catalyst support, a manufacturing method thereof, and a fuel cell using the same.

Hydrogen, which is in the spotlight as a next-generation eco-friendly energy source, is attracting attention as a power source that leads the transition to a hydrogen economic society, and one of these power sources, a polymer electrolyte membrane fuel cell (PEMFC), is a fuel cell that combines hydrogen and oxygen as fuel. It is an energy conversion device that can convert chemical energy that can be used for transportation and building power generation into electrical energy by using the electricity generated during the combining process.

The operating principle of a fuel cell is that fuel (hydrogen, methanol, etc.) is supplied to the anode, the fuel is oxidized by a catalyst action, electrons are released and conducted to the cathode through an external load, and at the cathode, the oxidant is reduced again by a catalyst action. Electricity is generated while generating water (non-patent literature, Yun Wang et al., Applied Energy 88 (2011) 981-1007).

The main research areas of fuel cell catalysts are research on manufacturing them at a size of several nanometers to increase catalyst activity and research on supporting them evenly on a carbon support with a high specific surface area to enable mass transfer and reaction with high efficiency. At this time, the carbon support serves to maximize reaction efficiency by inducing highly dispersed support of platinum nanoparticles, which are catalytic active sites, and to smoothly transfer electrons generated by the catalytic reaction to the output device.

Carbon black is generally used as a carbon carrier. However, when driving a fuel cell, the external air flowing into the electrode during the start and stop process mixes with the hydrogen, which is the fuel, and a high potential of 1.2V or higher affects the carbon. Due to a potential higher than 0.207V, which is the standard oxidation potential of carbon, the carbon causes corrosion. This shortens the performance and lifespan of the fuel cell.

As a countermeasure to this, attempts are being made to increase the crystallinity of the surface of the carbon support through high-temperature graphitization to increase the oxidation initiation temperature of the original carbon, thereby suppressing corrosion caused by fuel cell electrode deterioration.

As another method, metal oxides with high resistance to oxidation, such as CeO ₂ , SiO ₂ , NiO, SnO ₂ , TiO ₂ , ZrO ₂ , Ga ₂ O _{2 ,} etc. are considered as alternatives to carbon supports, of which TiO ₂ is Much research is being conducted as a catalyst support because of its low cost, abundance, non-toxicity, and high stability against acid and base.

In particular, TiO ₂ -supported Pt catalysts show higher catalytic stability compared to carbon-based supported catalysts after catalyst deterioration protocols due to the high oxidation resistance of TiO ₂ , and TiO ₂ supports are considered to be a material that ultimately increases electrochemical durability.

However, the Pt/TiO ₂ catalyst shows low oxygen reduction reaction activity, which appears to be due to the inhibition of the flow of electrons generated during the oxygen reduction reaction due to the low electrical conductivity of the insulating characteristics of TiO ₂ .

Accordingly, in order to complement the insulating characteristics of TiO ₂ , research is being conducted to increase electron transfer efficiency by physically mixing carbon with relatively high conductivity with TiO ₂ , but micron-sized TiO ₂ and carbon aggregates are mixed unevenly, creating a problem within the electrode. There is a problem that it causes defects in the electron transfer path and ultimately causes the performance of the membrane electrode assembly to deteriorate.

One purpose of the present invention is to provide a catalyst for oxidation-resistant fuel cells with excellent electrical conductivity of the catalyst support and a method for manufacturing the same in order to solve the above problems.

In order to achieve the above object, the present invention includes the steps of forming a carbon support dispersion solution, mixing a first metal precursor solution with the carbon support dispersion solution to form a first metal precursor mixed solution, and mixing the first metal precursors. Supporting a first metal by irradiating an electron beam to a solution, injecting a second metal precursor into the mixed solution containing the first metal, irradiating an electron beam to the mixed solution into which the second metal precursor is injected to form a second metal. A method for producing a fuel cell catalyst is provided, including the steps of supporting a metal and obtaining a carbon support on which the second metal is supported.

In another aspect, the present invention provides that the carbon support is selected from reduced graphene oxide, graphene, graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nanofibers, acetylene black, and furnace black. A method for manufacturing a fuel cell catalyst comprising one or more carbon supports is provided.

In another aspect, the present invention provides that the first metal precursor is a metal oxide precursor, and is an oxide selected from TiO ₂ , SnO ₂ , ZnO, VO ₂ , In ₂ O ₂ , NiO, MoO ₂ , WO ₂ , and CuO A method for manufacturing a fuel cell catalyst including one or more precursors is provided.

In another aspect, the present invention provides that the first metal precursor is TiCl ₄ , C ₁₂ H ₂₈ O ₄ Ti, Ti(OC ₂ H ₅ ) ₄ , Ti(OBu) ₄ , C ₁₂ H ₂₈ O ₄ Ti, and [( CH ₃ ) ₂ CHO] ₂ Ti(C ₅ H ₇ O ₂ ) ₂ A method for producing a fuel cell catalyst containing one or more selected from the group is provided.

In another aspect, the present invention provides a method of manufacturing a fuel cell catalyst in which the pH of the first metal precursor mixed solution is adjusted to be basic in the step of forming the first metal precursor mixed solution.

In another aspect, the present invention provides a method for manufacturing a fuel cell catalyst in which the electron beam irradiation time in the step of supporting the first metal is 30 minutes or less.

In another aspect, the present invention provides a method of manufacturing a fuel cell catalyst in which the size of the supported first metal in the step of supporting the first metal is 50 nm or less.

In another aspect, the present invention provides a method for manufacturing a fuel cell catalyst in which the second metal precursor is a platinum (Pt) precursor.

In another aspect, the present invention provides a method for manufacturing a fuel cell catalyst in which the second metal precursor is injected by an in-situ method.

In another aspect, the present invention provides a method of manufacturing a fuel cell catalyst in which the pH of the mixed solution is adjusted to basic in the step of injecting the second metal precursor.

In another aspect, the present invention provides a method for manufacturing a fuel cell catalyst in which the electron beam irradiation time in the step of supporting the second metal is 20 minutes or less.

In another aspect, the present invention provides a method for producing a fuel cell catalyst wherein the step of obtaining the carbon support on which the second metal is supported includes filtering the mixed solution irradiated with the electron beam and then drying it.

In another aspect, the present invention provides a fuel cell catalyst manufactured by the above manufacturing method.

In another aspect, the present invention provides a fuel cell including the fuel cell catalyst.

The fuel cell catalyst according to the present invention has oxidation resistance characteristics of metal oxides while maintaining the electrical conductivity of the carbon support. Accordingly, the catalytic activity of platinum particles, which are the active point of the fuel cell, can be improved, and the metal oxide prevents the platinum particles from directly interacting with the carbon support, which has the advantage of solving the carbon corrosion problem that occurs at the platinum/carbon interface. There is.

1 is a flowchart sequentially showing a method for manufacturing a fuel cell catalyst according to an embodiment of the present invention.
Figure 2 briefly shows a conventional fuel cell catalyst and a fuel cell catalyst according to an embodiment of the present invention.
Figure 3 shows transmission electron microscope (TEM) images of a fuel cell catalyst according to an embodiment of the present invention and a conventional fuel cell catalyst.
Figure 4 shows the results of X-ray diffraction pattern analysis (XRD) for a carbon support on which TiO ₂ was supported according to an embodiment of the present invention.
Figure 5 shows the results of thermogravimetric analysis (TGA) on a carbon support on which TiO ₂ was supported according to an embodiment of the present invention.
Figure 6 shows the results of thermogravimetric analysis of commercial carbon black and a fuel cell catalyst according to an embodiment of the present invention.
Figure 7 shows the results of analyzing the performance of the fuel cell catalyst according to an embodiment of the present invention and the existing fuel cell catalyst.
Figure 8 shows the results of evaluating the electrical conductivity of _{a mixture of TiO 2 supported} on a carbon support and an existing carbon support according to an embodiment of the present invention.

One embodiment of the present invention is shown in the accompanying drawings. However, this creative idea can be embodied in many different forms, and should not be construed as limited to the embodiments described in this specification. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present creative idea to those skilled in the art. Like reference numerals refer to like elements.

The terms used in this specification are intended to describe only specific embodiments and are not intended to limit the creative idea. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms, including “at least one,” unless the content clearly dictates otherwise. “At least one” should not be construed as limiting to the singular. As used herein, the term “and/or” includes any and all combinations of one or more of the listed items. As used in the detailed description, the terms "comprise" and/or "comprising" specify the presence of a specified feature, area, integer, step, operation, component and/or component, and one or more other features, areas, integers, or elements. , does not exclude the presence or addition of steps, operations, components, ingredients and/or groups thereof.

Unless otherwise defined, all terms (including technical and scientific terms) used in this specification have the same meaning as commonly understood by those skilled in the art to which this disclosure pertains. Additionally, it is also understood that terms as defined in commonly used dictionaries should be interpreted as having meanings consistent with their meanings within the context of the related art and present disclosure, and should not be interpreted in an idealized or overly formal sense. It will be.

Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents not currently contemplated or foreseen may occur to applicants or those skilled in the art. Accordingly, the appended claims, as filed and as modified, are intended to cover all such alternatives, modifications, variations, improvements and substantial equivalents.

In the following embodiments, terms such as first and second are used not in a limiting sense but for the purpose of distinguishing one component from another component.

In the following examples, singular terms include plural terms unless the context clearly dictates otherwise.

In cases where an embodiment can be implemented differently, a specific process sequence may be performed differently from the described sequence. For example, two processes described in succession may be performed substantially at the same time, or may be performed in an order opposite to that in which they are described.

1 is a flow chart sequentially showing a method for manufacturing a fuel cell catalyst according to an embodiment of the present invention.

Referring to Figure 1, the present invention includes forming a carbon support dispersion solution (S100), forming a first metal precursor mixed solution (S200), supporting the first metal (S300), and second metal precursor. A method for producing a fuel cell catalyst is provided, including the steps of injecting (S400), supporting a second metal (S500), and obtaining a carbon support on which the second metal is supported (S600).

In one embodiment of the present invention, the step of forming a carbon support dispersion solution (S100) is a step of dispersing the carbon support in a solvent.

The carbon support includes one or more carbon supports selected from reduced graphene oxide, graphene, graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nanofibers, acetylene black, and furnace black. can do.

The solvent may be a mixed solvent of water and alcohol. The alcohol contained in the solvent is preferably a polyhydric alcohol, and one or more selected from acetone, ethanol, isopropyl alcohol, ethanol, n-propyl alcohol, butanol, ethylene glycol, diethylene glycol, and glycerol can be used. there is.

To prepare the carbon support dispersion solution, a commonly used dispersion process may be used, for example, it may be produced through an ultrasonic dispersion process. This dispersion process can be carried out under the conditions of 3 seconds on and 1 second off and Amplitude intensity of 50% or less.

The step of forming a first metal precursor mixed solution (S200) is a step of forming a first metal precursor mixed solution by mixing the first metal precursor solution with the carbon support dispersion solution.

The first metal precursor is a metal oxide precursor and may include one or more oxide precursors selected from TiO ₂ , SnO ₂ , ZnO, VO ₂ , In ₂ O ₂ , NiO, MoO ₂ , WO ₂ , and CuO. Specifically, the first metal precursor is TiCl ₄ , C ₁₂ H ₂₈ O ₄ Ti, Ti(OC ₂ H ₅ ) ₄ , Ti(OBu) ₄ , C ₁₂ H ₂₈ O ₄ Ti, and [(CH ₃ ) ₂ CHO] ₂ Ti(C ₅ H ₇ O ₂ ) ₂ It may include one or more selected from the group consisting of, but is not limited thereto.

The first metal precursor mixed solution may be formed by injecting the first metal precursor solution into the carbon support dispersion solution. The rate of infusion may be 5 to 20 mL/min.

Meanwhile, the pH of the first metal precursor mixed solution may be adjusted to be basic.

At this time, there is no particular limitation as long as the method can adjust the pH, and the pH can be adjusted by injecting a fixed amount of a pH adjuster. At least one of common pH adjusters such as NaOH, KOH, and aqueous ammonia may be used, but the pH is not limited thereto, and the pH range may be pH 7 to 14. Preferably, pH can be adjusted to 7 to 8 using 1 M NaOH.

The step of supporting the first metal (S300) is a step of irradiating an electron beam to the first metal precursor mixed solution.

The electron beam may have energy of 0.1 to 2 MeV, and the applied current may be 0.1 to 20 mA. When an electron beam is irradiated under the above conditions, ions of the first metal are reduced and the first metal is supported on the carbon support.

The electron beam irradiation time is not less than 1 minute but not more than 30 minutes; Not less than 1 minute but not more than 25 minutes; More than 1 minute and less than 20 minutes; More than 1 minute and less than 15 minutes; It may be 1 minute or more and 10 minutes or less, or 1 minute or more and 5 minutes or less, and preferably 1 minute or more and 5 minutes or less.

In the step of irradiating the electron beam, the electron beam may be irradiated for an appropriate time depending on the type of the first metal.

In the step of supporting the first metal, the size of the supported first metal is 1 to 50 nm; 1 to 40 nm; 1 to 30 nm; 1 to 20 nm; 1 to 10 nm; 5 to 50 nm; 5 to 40 nm; 5 to 30 nm; 5 to 20 nm; 5 to 10 nm; 10 to 50 nm; 10 to 40 nm; 10 to 30 nm; 10 to 20 nm; 15 to 50 nm; 15 to 40 nm; It may be 15 to 30 nm or 15 to 20 nm.

When the first metal is supported in the above-mentioned size, the physical distance from the carbon support becomes closer, and the movement distance of electrons is shortened, thereby solving the problem of low electrical conductivity of the first metal.

The step of injecting the second metal precursor (S400) is a step of injecting the second metal precursor into the first metal precursor mixed solution carrying the first metal.

The second metal precursor may be a platinum (Pt) precursor. The platinum precursors include H ₂ PtCl ₆ , H ₆ Cl ₂ N ₂ Pt, PtCl ₂ , PtBr ₂ , platinum acetylacetonate, K ₂ (PtCl ₄ ), H ₂ Pt(OH) ₆ , Pt ( NO ₃ ) ₂ , [Pt(NH ₃ ) ₄ ]Cl ₂ , [Pt(NH ₃ ) ₄ ](HCO ₃ ) ₂ , [Pt(NH ₃ ) ₄ ](OAc) ₂ , (NH ₄ ) ₂ PtBr ₆ At least one selected from the group consisting of , (NH ₃ ) ₂ PtCl ₆ and their hydrates may be used, but is not limited thereto.

The step of injecting the second metal precursor may be performed using an in-situ method, but is not limited thereto. The rate of infusion may be 5 to 20 mL/min.

According to one embodiment, when platinum ions are injected in-situ, a highly durable fuel cell catalyst can be manufactured by synthesizing an oxidation-resistant catalyst support in a short time by inducing reduction of platinum by continuously generated accelerated electrons.

The step of injecting the second metal precursor may include adjusting the pH of the mixed solution to basic. At this time, there is no particular limitation as long as the method can adjust the pH, and the pH can be adjusted by injecting a fixed amount of a pH adjuster. At least one of common pH adjusters such as NaOH, Na ₂ CO ₃ , KOH, K ₂ CO ₃ and H ₂ SO ₄ may be used, but is not limited thereto, and the pH range may be pH 7 to 14. Preferably, pH can be adjusted to 10 to 11 using 1 M NaOH.

The step of supporting the second metal (S500) is a step of alloying the second metal by irradiating an electron beam to the mixed solution into which the second metal precursor is injected.

The electron beam may have energy of 0.1 to 2 MeV, and the applied current may be 0.1 to 20 mA. When an electron beam is irradiated under the above conditions, ions of the second metal are reduced and the second metal is alloyed into the carbon support.

The electron beam irradiation time is 10 seconds or more and 20 minutes or less; More than 10 seconds and less than 15 minutes; More than 10 seconds and less than 10 minutes; It may be 10 seconds or more and 5 minutes or less, or 10 seconds or more and 1 minute or less, and preferably 1 minute or less. Depending on the type of second metal, the electron beam can be irradiated for an appropriate amount of time.

Obtaining the carbon support on which the second metal is supported (S600) is a step of obtaining a fuel cell catalyst on which the second metal is supported. This step may include filtering and drying the precursor mixture solution irradiated with the electron beam. There is no particular limitation as to the method of filtration, but filtration may be performed using a vacuum filter. There is no particular limitation as to the drying method, and drying may be performed in an oven. As an example, when drying in an oven, drying can be done at a temperature of 100°C or lower, preferably 60°C.

Figures 2 (a) to (c) are diagrams briefly showing a conventional fuel cell catalyst and a fuel cell catalyst according to an embodiment of the present invention. In Figure 2, (a) is a conventional platinum/carbon catalyst, (b) is a catalyst in which platinum is supported on a physically mixed TiO ₂ /carbon support, and (c) is a fuel cell catalyst according to the present invention.

The platinum/carbon catalyst according to (a) of FIG. 2 is known to have platinum metal eluted and aggregated due to oxidation of the carbon support during accelerated deterioration, accelerating the decline in platinum utilization and performance.

Figure 2 (b) is a catalyst in which platinum is supported after simply mixing micron-sized giant TiO ₂ aggregates with a carbon support. Since carbon and TiO ₂ aggregates are unevenly mixed, the electron movement path generated during the oxygen reduction reaction is suppressed by the TiO ₂ aggregates, which are considered insulators, and may cause performance degradation.

On the other hand, as shown in (c) of FIG. 2, in the fuel cell catalyst manufactured by electron beam irradiation according to an embodiment of the present invention, TiO ₂ particles are nanosized and the physical distance from carbon becomes closer, which shortens the electron transfer distance. Through this effect, the low electrical conductivity of TiO ₂ can be solved. Additionally, by preventing platinum particles from interacting directly with the carbon support, it can solve the problem of carbon corrosion occurring at the platinum/carbon interface, which is known to reduce the durability of existing catalysts.

Another aspect of the present invention provides a fuel cell catalyst manufactured by the above manufacturing method and a fuel cell including the fuel cell catalyst.

The fuel cell may be a polymer electrolyte fuel cell, and the membrane electrode assembly of the polymer electrolyte fuel cell includes an anode, a cathode, and a polymer electrolyte membrane between them, and at least one of the anode and the cathode may contain the catalyst of the present invention. You can.

Hereinafter, the present invention will be described in detail through experimental examples.

However, the experimental examples described below only specifically illustrate the present invention from one aspect, and the present invention is not limited thereto.

<Experimental Example 1> Transmission Electron Microscope (TEM) Analysis

After physically mixing TiO ₂ with a size of 50 nm or more and a carbon support, TEM was analyzed for a platinum-supported fuel cell catalyst (comparative example) and a fuel cell catalyst according to an embodiment of the present invention (example).

The experimental results are shown in Figures 3 (a) and (b) for the comparative examples, and in Figures 3 (c) and (d) for the examples.

Looking at Figures 3 (a) and (b), micron-sized TiO ₂ is mixed in the carbon support, and platinum particles are supported unevenly on the TiO ₂ and carbon surfaces. Ultimately, as shown in (b) of FIG. 2, it is believed that the platinum catalyst supported on the surface of TiO ₂ , which has insulating properties, will result in loss of electrochemical performance due to the inhibition of the movement path of electrons generated during the oxygen reduction reaction.

On the other hand, looking at (c) and (d) of Figure 3, TiO ₂ nanoparticles of about 10 nm in size are uniformly mixed in the carbon support, and platinum particles are also uniformly supported on the nanosized TiO ₂ /C composite. It is observed that As shown in (c) of FIG. 2, TiO ₂ is supported uniformly, thereby suppressing agglomeration between metals when manufacturing a platinum catalyst. In addition, by nano-izing the particle size of TiO ₂ , it is expected to shorten the path of electrons generated during the oxygen reduction reaction on the platinum surface, thereby lowering electrical resistance and suppressing electrochemical performance loss.

<Experimental Example 2> X-ray diffraction pattern analysis (XRD)

According to an embodiment of the present invention, X-ray diffraction pattern analysis was performed on a carbon support (TiO ₂ /C) on which TiO ₂ was supported, and the experimental method was as follows.

X-ray diffraction pattern analysis was performed on the carbon support using Rigaku 1200, Cu-Kα light source, and Ni β-filter at 40 kV and 20 mA. The average grain size of carbon was determined from the 2θ reflection peak for the graphite lattice plane using the Debye-Scherer equation.

The experimental results are shown in Figure 4. Looking at Figure 4, the synthesized TiO ₂ /C composite can be confirmed as an anatase TiO ₂ phase, and after platinum loading (Pt/TiO ₂ /C), the face-centered cubic shape of platinum is observed at 39.6 ^o , 46.1 ^o , 67.1 ^o , and 80.9 ^o. The structure (fcc; face-centered cubic) was observed.

<Experimental Example 3> Thermogravimetric analysis (TGA)

According to one embodiment of the present invention, thermogravimetric analysis was performed on a carbon support (TiO ₂ /C) on which TiO ₂ was supported by adjusting the content of TiO ₂ , and the results of the experiment are shown in FIG. 5. Looking at Figure 5, it can be seen that 2.05 wt%, 3.14 wt%, and 5.1 wt% titanium dioxide were supported, respectively.

Meanwhile, thermogravimetric analysis was performed on commercial carbon black and a catalyst carrying 50 wt% of platinum on a TiO ₂ /C composite according to the present invention, and the results of the experiment are shown in FIG. 6. The TiO ₂ /C composite used a support containing 3 wt% of TiO ₂ , and looking at Figure 6, the metal loading amount after platinum loading was confirmed to be 53.05%.

<Experimental Example 4> Performance evaluation of fuel cell catalyst

Regarding the fuel cell catalyst according to an embodiment of the present invention (Example, 50 wt% Pt/TiO ₂ /C) and the existing fuel cell catalyst with platinum supported on an existing carbon support (comparative example, 50 wt% Pt/C) The performance of the unit cells was compared and analyzed using cyclic voltammetry.

The experimental results are shown in Figure 7. Looking at FIG. 7, the initial ECSA performance of the Example and Comparative Example was confirmed to be similar at 94.2 m ² /g and 95.8 m ² /g, respectively, which is expected to maintain the platinum utilization rate even in the presence of insulating TiO ₂ .

After further evaluation of catalyst deterioration, the reduction rate of performance compared to the initial ECSA performance was 28.3% in Example and 53.8% in Comparative Example. This is believed to be because the nano-oxidation-resistant TiO ₂ suppresses corrosion of carbon generated during deterioration and improves the durability of the membrane electrode assembly while maintaining the dispersibility of platinum particles.

<Experimental Example 5> Nanoscale TiO ₂ /Evaluation of carbon composite electrical conductivity

Four for the nano-ized TiO ₂ /carbon composite (electron beam-based synthesized composite, Example) and the mixture in which TiO ₂ was supported on an existing carbon support (carbon-TiO ₂ simple mixture, comparative example) according to an embodiment of the present invention -Comparative analysis was conducted using probe conductivity.

The experimental results are shown in Figure 8. The electrical conductivity of each catalyst support was analyzed as the applied pressure increased. Looking at Figure 8, the electrical conductivity of TiO ₂ oxide was confirmed to be similar to 8.86 x 10 ^-5 S/cm even as the pressure increased from the initial 2.33 x 10 ^-5 S/cm, which is analyzed to be due to insulating TiO ₂ .

The initial conductivity of the Example and Comparative Example was confirmed to be 0.52 and 0.17 S/cm, respectively, and when the pressure increased to 20 MPa, it was 9.63 and 5.11 S/cm, respectively. The improvement in electrical conductivity despite the presence of insulating TiO ₂ is due to the fact that carbon is mixed in the support. In particular, it is believed that the improvement in electrical conductivity in the Examples compared to the Comparative Examples was caused by reducing the electrical resistance distance due to nano-sized TiO ₂ .

As such, the present invention has been described with reference to an embodiment shown in the drawings, but this is merely illustrative and those skilled in the art will understand that various modifications and variations of the embodiment are possible therefrom. . Therefore, the true scope of technical protection of the present invention should be determined by the technical spirit of the attached patent claims.

Claims (14)

forming a carbon support dispersion solution;
mixing a first metal precursor solution with the carbon support dispersion solution to form a first metal precursor mixed solution;
supporting a first metal by irradiating an electron beam to the first metal precursor mixed solution;
Injecting a second metal precursor into the mixed solution containing the first metal;
supporting a second metal by irradiating an electron beam to the mixed solution into which the second metal precursor is injected; and
A method for producing a fuel cell catalyst, comprising obtaining a carbon support on which the second metal is supported.
According to claim 1,
The carbon support includes one or more carbon supports selected from reduced graphene oxide, graphene, graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nanofibers, acetylene black, and furnace black. Method for producing a fuel cell catalyst.
According to claim 1,
The first metal precursor is a precursor of a metal oxide,
A method for producing a fuel cell catalyst, comprising at least one oxide precursor selected from TiO ₂ , SnO ₂ , ZnO, VO ₂ , In ₂ O ₂ , NiO, MoO ₂ , WO ₂ , and CuO.
According to claim 1,
The first metal precursor is TiCl ₄ , C ₁₂ H ₂₈ O ₄ Ti, Ti(OC ₂ H ₅ ) ₄ , Ti(OBu) ₄ , C ₁₂ H ₂₈ O ₄ Ti, and [(CH ₃ ) ₂ CHO] ₂ A method for producing a fuel cell catalyst, comprising at least one selected from Ti(C ₅ H ₇ O ₂ ) ₂ .
According to claim 1,
In the step of forming the first metal precursor mixed solution, the pH of the first metal precursor mixed solution is adjusted to be basic.
According to claim 1,
A method for producing a fuel cell catalyst, wherein the time for irradiating the electron beam in the step of supporting the first metal is 30 minutes or less.
According to claim 1,
In the step of supporting the first metal, the size of the supported first metal is 50 nm or less.
According to claim 1,
A method for producing a fuel cell catalyst, wherein the second metal precursor is a platinum (Pt) precursor.
According to claim 1,
A method for producing a fuel cell catalyst, wherein the second metal precursor is injected by an in-situ method.
According to claim 1,
In the step of injecting the second metal precursor, the pH of the mixed solution is adjusted to be basic.
According to claim 1,
A method for producing a fuel cell catalyst, wherein the time for irradiating the electron beam in the step of supporting the second metal is 20 minutes or less.
According to claim 1,
The step of obtaining the carbon support on which the second metal is supported includes filtering and then drying the mixed solution irradiated with the electron beam.
A fuel cell catalyst manufactured by the manufacturing method of any one of claims 1 to 12.
According to claim 13,
A fuel cell comprising the fuel cell catalyst.

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