KR20210130031A - Electrode catalyst, manufacturing method thereof and fuel cell using the same - Google Patents

Abstract

The present invention relates to an electrode catalyst, a method for manufacturing the same, and a fuel cell using the same. Provided are an electrode catalyst, a method for manufacturing the same, and a fuel cell using the same, wherein the electrode catalyst comprises: a carbon layer that increases electron affinity of a catalyst by fluorine to increase catalytic activity and is complexly doped with nitrogen and fluorine to improve stability by carbon coating; and a transition metal.

Description

Electrode catalyst, manufacturing method thereof, and fuel cell using same

The present invention relates to an electrode catalyst, a method for manufacturing the same, and a fuel cell using the same, and more particularly, an electrode catalyst comprising a carbon coating layer doped with nitrogen and fluorine and a transition metal core layer, thereby improving oxygen reduction reaction characteristics and stability and a method for manufacturing the same, and a fuel cell using the same.

A fuel cell is an energy conversion device that converts chemical energy of hydrocarbon fuels such as hydrogen or methanol into electrical energy using an electrochemical reaction. Since energy is converted through a direct chemical reaction with oxygen, the efficiency is high and the emission of pollutants is high. It has the advantage of being an eco-friendly energy device.

However, since fuel cells use expensive precious metals such as platinum nanoparticles as catalysts for chemical reactions, the cost of fuel cells increases, and deterioration such as aggregation of platinum nanoparticles occurs during long-term operation, making it difficult to create related markets. are suffering

Therefore, the development of an alternative catalyst material having a low cost and high durability that can improve these problems is required for the development of the fuel cell industry.

In the early stage of the fuel cell catalyst development process, only noble metals such as platinum, palladium, and iridium were mainly studied, and carbon materials such as graphene and carbon nanotubes have been mainly used as highly durable support materials.

However, research is underway to impart activity to the Oxygen Reduction Reaction (ORR) in fuel cells by introducing transition metal elements such as cobalt and iron into the structure of the carbon material. It is attracting attention as a catalyst material.

Korean Patent Publication No. 10-1969547 Korean Patent Publication No. 10-2013-0039456

The present invention was created to improve the problems of the prior art, and includes an electrode catalyst having high activity for oxygen reduction reaction including a carbon material and a transition metal so as to replace an expensive noble metal catalyst, and a method for manufacturing the same and to provide a fuel cell using the same.

In order to achieve the above object, the electrode catalyst according to the present invention comprises: a catalytically active part exhibiting oxygen reduction activity; and a carbon support part supporting the catalytically active part and allowing electrons to move; and a carbon coating layer formed by coating the outside of the transition metal core layer to improve stability, wherein the carbon coating layer is doped with nitrogen and fluorine to improve oxygen reduction activity.

The transition metal core layer includes ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), vanadium (V), tungsten (W), cobalt (Co), At least from the group consisting of iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), cerium (Ce), and copper (Cu) It may include more than one.

The carbon coating layer may include at least one element from the group consisting of nitrogen (N), fluorine (F), boron (B), and sulfur (S) in order to increase the activity of the transition metal core layer.

The catalytically active portion may have a spherical, rod-shaped, linear or polyhedral shape so that the oxygen reduction reaction occurs on the surface.

In addition, the electrode catalyst manufacturing method according to the present invention comprises a polymer polymerization step of polymerizing a polymer composite by mixing a raw material containing an aniline monomer, an aniline monomer including fluorine, a transition metal precursor exhibiting oxygen reduction activity, and an oxidizing agent; a polymer drying step of drying the polymer composite; a carbonization step of carbonizing the dried polymer composite by heat treatment; an acid treatment step of acid-treating the electrode catalyst formed by carbonizing the polymer composite; and a heat treatment step of heat-treating the acid-treated electrode catalyst.

In the polymer polymerization step, raw materials including an aniline monomer, an aniline monomer including fluorine, a transition metal precursor exhibiting oxygen reduction activity, and an oxidizing agent are mechanically stirred to polymerize the polymer composite.

Transition metal precursors are ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), vanadium (V), tungsten (W), cobalt (Co), iron At least one selected from the group consisting of (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), cerium (Ce), and copper (Cu) It may be a compound containing the above elements.

The oxidizing agent may include an acid selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, or a sulfate selected from at least one selected from ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, and potassium sulfate.

In the polymer polymerization step, a compound containing at least one of nitrogen (N), fluorine (F), boron (B), and sulfur (S) may be further mixed with the raw material.

In the polymer polymerization step, the aniline monomer and the aniline monomer including fluorine are composed of 1:1 volume ratio or more and 1:100 volume ratio and stirred at a rotation speed of 10 rpm or more and 400 rpm or less for 5 minutes or more and 100 hours or less.

In the polymer polymerization step, a solution containing 0.1 M or more and 10 M or less of the oxidizing agent may be administered and stirred at a rotation speed of 10 rpm or more and 400 rpm or less for 5 minutes or more and 100 hours or less.

In the polymer drying step, it may be dried at 10 degrees or more and 80 degrees or less for 5 hours or more and 24 hours or less so that the solvent contained in the polymer composite is removed.

In the carbonization step, the polymer composite may be carbonized by heating it in a gas atmosphere containing at least one of nitrogen, hydrogen, or argon at a temperature of 300 degrees or more and 1000 degrees or less for 10 minutes or more and 24 hours or less.

In the acid treatment step, acid treatment can be carried out for 5 minutes or more and 24 hours or less by supporting it in a solution containing at least one of hydrochloric acid, sulfuric acid, nitric acid and perchloric acid in an amount of 0.1 M or more and 1 M or less so as to remove metal by-products from the carbonized electrode catalyst. have.

In the heat treatment step, the electrode catalyst may be heated in a gas atmosphere containing at least one of nitrogen, hydrogen, or argon at a temperature of 300 degrees or more and 1000 degrees or less for 10 minutes or more and 24 hours or less.

In addition, the fuel cell according to the present invention includes an anode including the electrode catalyst according to the present invention, an anode to which fuel is supplied, and a separator provided between the cathode and the anode, in which ions are movable.

As described above, according to the electrode catalyst, the method for manufacturing the same, and the fuel cell using the same according to the present invention, it includes a transition metal core in which oxygen reduction reaction occurs, and oxygen coated with a carbon layer complexly doped with nitrogen and fluorine on the surface. A reduction catalyst is provided.

Therefore, the electron affinity of the oxygen reduction reaction catalyst is increased by the doping source element, so that the catalytic activity is increased, and the stability is improved by coating the transition metal with carbon. to solve the problem of poor stability.

1 is an explanatory diagram illustrating a photograph of an electrode catalyst according to an embodiment of the present invention.
2 is a block diagram illustrating a method of manufacturing an electrode catalyst according to an embodiment of the present invention.
3 is a perspective view showing the structure of an electrode catalyst according to another embodiment of the present invention.
4 is a perspective view illustrating a structure of a fuel cell according to another embodiment of the present invention.
5 is a picture taken with a scanning electron microscope and analysis results of the shape of the electrode catalyst according to another embodiment of the present invention by EDX (Energy Dispersive X-ray microanalysis).
6 is a picture taken with a transmission electron microscope and an EDX analysis result of the shape of the catalytically active part constituting the electrode catalyst according to another embodiment of the present invention.
7 is a cyclic voltammetry (CV) and linear scanning method showing the electrochemical characteristics of the catalytically active part formed by varying the carbonization temperature in the method for forming an electrode catalyst according to an embodiment of the present invention in 0.1M potassium hydroxide electrolyte. It is a graph measured according to Linear Sweep Voltammetry (LSV).
8 shows electrochemical characteristics of a catalytically active part formed by varying the temperature of the carbonization step in the method for forming an electrode catalyst according to an embodiment of the present invention in 0.1 M perchloric acid electrolyte. Measured by cyclic voltammetry and linear scanning potential method; It is also a graph.
9 is a graph showing the results of measuring the stability of the catalytically active part on the electrode catalyst according to another embodiment of the present invention through an accelerated degradation test.
10 is a graph showing voltage/current curves of a proton ion exchange membrane fuel cell (PEMFC) cell and an anion ion exchange membrane fuel cell (AEMFC) cell using a proton ion exchange membrane or an anion ion exchange membrane in another embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. This is not intended to limit the present invention to specific embodiments, and should be construed to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In describing the present invention, terms such as first, second, etc. may be used to describe various components, but the components may not be limited by the terms. The above terms are only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

The term “and/or” may include a combination of a plurality of related listed items or any of a plurality of related listed items.

When a component is referred to as being “connected” or “connected” to another component, it may be directly connected or connected to the other component, but other components may exist in between. can be understood On the other hand, when it is mentioned that a certain element is "directly connected" or "directly connected" to another element, it may be understood that the other element does not exist in the middle.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression may include the plural expression unless the context clearly dictates otherwise.

In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, and one or more other features It may be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded in advance.

Unless defined otherwise, all terms used herein, including technical or scientific terms, may have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary may be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, it is interpreted in an ideal or excessively formal meaning. it may not be

In addition, the following embodiments are provided to more completely explain to those with average knowledge in the art, and the shapes and sizes of elements in the drawings may be exaggerated for clearer description.

Referring to FIG. 3 , the electrocatalyst according to an embodiment of the present invention includes a catalytically active part 10 exhibiting oxygen reduction activity and a carbon support 20 supporting the catalytically active part 10 and through which electrons are moved. and the catalytically active part 10 includes a transition metal core layer 11 in which a catalytic reaction occurs and a carbon coating layer 12 formed by coating the outside of the transition metal core layer 11 to improve stability, The carbon coating layer 12 is doped with nitrogen and fluorine to improve oxygen reduction activity.

More specifically, in the electrocatalyst, a carbon support portion 20 comprising a carbon material supports the catalytically active portion 10 , and the catalytically active portion 10 includes a transition metal core layer 11 in the center, and has carbon on the outside. As it is coated with , corrosion is prevented and stability is improved in the electrolyte environment of the fuel cell.

In addition, since the carbon coating layer 12 is doped with nitrogen and fluorine at the same time to increase the activity, it has the effect of accelerating the oxygen reduction reaction while protecting the transition metal core layer 11, so that it can replace the existing platinum catalyst and in the fuel cell. It can be operated stably for a long time.

The transition metal core layer 11 configured in the center of the catalytically active part 10 is ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), vanadium ( V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), cerium ( Ce) and at least one or more from the group consisting of copper (Cu), and most preferably, the transition metal core layer 11 may be configured to include metallic iron and carbon iron.

The carbon coating layer 12 on which the outer portion of the transition metal core layer 11 is coated is composed of nitrogen (N), fluorine (F), boron (B), sulfur (S), etc. in order to increase the activity of the transition metal core layer. It may be configured to include at least one or more from the group.

The catalytically active part 10 is characterized in that it has any one of a spherical shape, a rod shape, a linear shape, or a polyhedral shape so that the oxygen reduction reaction occurs on the surface.

1 and 2, the electrode catalyst manufacturing method according to another embodiment of the present invention is a polymer composite by mixing a raw material containing an aniline monomer, an aniline monomer including fluorine, a transition metal precursor exhibiting oxygen reduction activity, and an oxidizing agent. A polymer polymerization step (S10) of polymerizing the polymer composite, a polymer drying step (S20) of drying the polymer composite, a carbonization step of carbonizing the dried polymer composite by heat treatment (S30), acid treatment of the electrode catalyst formed by carbonizing the polymer composite It includes an acid treatment step (S40) and a heat treatment step (S50) of heat-treating the acid-treated electrode catalyst.

In detail, the electrode catalyst manufacturing method according to another embodiment of the present invention is mixed using at least one mixing method such as a turbo mill, a super micron mill, a roller mill, a Raymond mill, a pot mill, a jet mill, a ball mill, etc. Directly, they can be mixed using a ball mill that is inexpensive to install and operate and can handle a variety of materials with relative ease.

The ceramic ball used in the ball mill is characterized by using alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), silica (SiO ₂ ), and stainless steel (Stainless steel) strong against external impact.

In the polymer polymerization step (S10), the raw material is stirred using a mixing method such as a ball mill, and then the polymer composite is polymerized through an oxidizing agent.

In detail, the transition metal precursor is ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), vanadium (V), tungsten (W), cobalt ( Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), cerium (Ce) and copper (Cu) It can be used including a compound containing at least one element from the group.

The oxidizing agent may include an acid selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, or a sulfate selected from at least one selected from ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, and potassium sulfate.

In the polymer polymerization step (S10), a compound containing at least one or more of nitrogen (N), fluorine (F), boron (B), and sulfur (S) is further mixed with the raw material so that heterogeneous elements are mixed with the carbon coating layer 12 ) can be formed.

In the polymer polymerization step (S10), the aniline monomer and the aniline monomer including fluorine are composed of 1:1 volume ratio or more and 1:100 volume ratio and stirred at a rotation speed of 10 rpm or more and 400 rpm or less for 5 minutes or more and 100 hours or less.

When the ratio of the aniline monomer and the aniline monomer including fluorine is less than 1:1 by volume, the polymer is mainly formed of aniline, so that fluorine may not be sufficiently contained.

In addition, if the rotation speed is less than 10 rpm, the raw material is not sufficiently stirred, and if it is more than 400 rpm, the temperature is unnecessarily increased due to friction between the raw materials during the mixing process, which may cause an unwanted reaction.

In addition, if the stirring time is less than 5 minutes, the raw material is not sufficiently stirred, and if it is more than 100 hours, no further improvement in properties can be observed, so the necessity is reduced.

In the polymer polymerization step (S10), a solution containing 0.1 M or more and 10 M or less of the oxidizing agent may be administered and stirred at a rotation speed of 10 rpm or more and 400 rpm or less for 5 minutes or more and 100 hours or less.

When the oxidizing agent is less than 0.1M, the desired polymer composite is not formed through sufficient oxidation, and when it exceeds 10M, the oxidizing agent remains excessively and is wasted even after the formation of the polymer composite is sufficiently completed.

In addition, when the rotation speed is less than 10 rpm, the raw material is not sufficiently stirred, and when it is more than 400 rpm, the temperature is unnecessarily increased due to friction between the raw materials in the polymerization process, and unwanted reactions may occur.

In addition, if the polymerization time is less than 5 minutes, the polymerization reaction is incomplete, and if it is more than 100 hours, the reaction is sufficiently completed and there is no additional reaction, thereby reducing the need.

In the polymer drying step (S20), it may be dried at 10 degrees or more and 80 degrees or less for 5 hours or more and 24 hours or less so that the solvent contained in the polymer composite is removed.

If the temperature is less than 10 degrees, it is difficult to dry the solvent, and at 80 degrees or more, deformation of the polymer may occur.

In addition, if it is less than 5 hours, the solvent is not sufficiently dried and removed, and if it exceeds 24 hours, drying is completed, thereby reducing the need.

In the carbonization step (S30), the polymer composite may be carbonized by heating it in a gas atmosphere containing at least one of nitrogen, hydrogen, or argon at a temperature of 300 degrees or more and 1000 degrees or less for 10 minutes or more and 24 hours or less.

If the polymer composite is treated at less than 300 degrees, it may not be sufficiently carbonized, and if it exceeds 1000 degrees, the bonds may be separated and the carbon layer may not be formed or the metal may be melted and damaged.

In addition, when heated for less than 10 minutes, it may not be sufficiently carbonized, and when it exceeds 24 hours, it is difficult to expect additional carbonization.

In the acid treatment step (S40), the acid treatment step (S40) is carried out in a solution containing at least one of hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid in an amount of 0.1 M or more and 1 M or less so as to remove metal by-products from the carbonized electrode catalyst for 5 minutes or more and 24 hours or less. can be processed

If a solution containing less than 0.1 M of acid is used, metal by-products will not be sufficiently removed, and if it is more than 1 M, excessive metal corrosion or other effects may occur.

In addition, if the treatment is less than 5 minutes, the metal by-product is not sufficiently removed, and if it proceeds for more than 24 hours, the metal by-product is sufficiently removed, thereby reducing the need.

In the heat treatment step (S50), the electrode catalyst may be heated in a gas atmosphere containing at least one of nitrogen, hydrogen, or argon at a temperature of 300 degrees or more and 1000 degrees or less for 10 minutes or more and 24 hours or less.

If the electrocatalyst is treated at less than 300°C, the properties are deteriorated due to insufficient heat treatment, and if it exceeds 1000°C, the metal may be melted and damaged.

In addition, when heated for less than 10 minutes, heat treatment is not sufficiently performed, and when it exceeds 24 hours, it is difficult to expect additional effects due to heat treatment.

In addition, referring to FIG. 4 , a fuel cell 100 according to another embodiment of the present invention includes an anode 120 including the electrode catalyst according to the present invention, an anode 110 to which fuel is supplied, and the cathode 120 . and the separation membrane 130 provided between the anode 110 and the ion movement.

The anode 110 may use a catalyst including at least one selected from among platinum (Pt), platinum-iron alloy (PtFe), and platinum-cobalt alloy (PtCo) so as to have excellent skin toxicity by fuel, and the most Preferably, platinum (Pt) may be included.

The fuel used for the anode 110 may be hydrogen, alcohol including methanol, ethanol, and hydrocarbons including natural gas, methane, propane, butane, and the like.

The cathode 120 includes the electrode catalyst according to the present invention and is formed so that external air containing oxygen can flow.

The separation membrane 130 provided between the cathode 120 and the anode 110 is at least any one of a perfluorocarbon series such as Nafion, which has high ionic conductivity, or a sulfonated heat-resistant polymer containing a sulfonic acid group ion to rapidly transfer protons. It may be formed to include one or more.

In addition, the separation membrane 130 is a solution containing at least one of salts such as ammonium, pyridinium, phosphonium, sodium, guanidinium, etc. to rapidly transfer anions polyethylene or polypropylene, polyvinylidene fluoride (Polyvinylidene) Fluoride) or may be formed in the form of a polymer electrolyte containing salt.

5, in the carbonization step (S30) of the electrocatalyst manufacturing method according to another embodiment of the present invention, the shape of the electrode catalyst prepared by varying the carbonization temperature is taken with a scanning electron microscope and EDX (Energy Dispersive X) -ray microanalysis) analysis result can be confirmed.

The carbonization step was carried out at a temperature condition of (a) 800 degrees, (b) 900 degrees, (c) 950 degrees, and (d) 1000 degrees, respectively, and the prepared electrode catalysts were (a) NFC@Fe/Fe3C-8, (b)NFC@Fe/Fe3C-9, (c)NFC@Fe/Fe3C-9.5 and (d)NFC@Fe/Fe3C-10.

According to the SEM analysis photo (ad), it can be confirmed that each catalytically active part 10 particles are dispersed and formed on the carbon support part 20, while the fluorine atoms are distributed close to the metal, while the nitrogen atoms are all It can be seen that they are uniformly distributed over the area.

Referring to FIG. 6 , the catalytically active part 10 of the NFC@Fe/Fe3C-9 electrocatalyst manufactured by the method for preparing an electrocatalyst according to another embodiment of the present invention includes carbon on the outside of the transition metal core layer 11 . It can be confirmed that the coating layer 12 is formed, and it is confirmed that the thickness is formed at a level of about 10 nm.

In addition, nitrogen is distributed over the carbon coating layer 12 and the carbon support 20 outside the transition metal core layer 11, while fluorine is concentrated in the carbon coating layer 12 outside the transition metal core layer 11, It can be confirmed that there is

Referring to FIG. 7 , in the method for forming an electrode catalyst according to an embodiment of the present invention, the carbonization temperature ((a) 800 degrees, (b) 900 degrees, (c) 950 degrees, (d) 1000 degrees) is varied. Electricity of one electrocatalyst ((a)NFC@Fe/Fe3C-8, (b)NFC@Fe/Fe3C-9, (c)NFC@Fe/Fe3C-9.5, (d)NFC@Fe/Fe3C-10) It can be seen a graph measuring chemical properties in 0.1M potassium hydroxide electrolyte according to Cyclic Voltammetry and Linear Sweep Voltammetry.

When referring to the graph (dashed line: argon condition, solid line: oxygen condition), the result of measuring the electrochemical properties of the electrode catalyst in the range of 0.03V to 1.13V in the 0.1M potassium hydroxide electrolyte condition compared to the platinum/carbon reference electrode, NFC@Fe The electrochemical activity of the /Fe3C transition metal core layer 11 can be confirmed under all conditions.

In addition, referring to the LSV curve, it can be seen that the NFC@Fe/Fe3C-9 electrode catalyst heat-treated at 900 degrees showed superior properties than carbonized at other temperatures, showing the closest properties to platinum.

8, in the method for forming an electrode catalyst according to an embodiment of the present invention, the carbonization temperature ((a) 800 degrees, (b) 900 degrees, (c) 950 degrees, (d) 1000 degrees) is varied. of one catalytically active part ((a)NFC@Fe/Fe3C-8, (b)NFC@Fe/Fe3C-9, (c)NFC@Fe/Fe3C-9.5, (d)NFC@Fe/Fe3C-10) A graph of electrochemical properties measured in 0.1M perchloric acid electrolyte according to Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) can be seen.

Compared with the platinum/carbon reference electrode, the electrochemical properties of the electrode catalyst were measured in the range of 0.03V to 1.13V in the 0.1M perchlorate electrolyte electrolyte condition. Referring to the graph (dashed line: argon condition, solid line: oxygen condition), The electrochemical activity of the /Fe3C transition metal core layer 11 can be confirmed under all conditions.

In addition, referring to the LSV curve, it was confirmed that the NFC@Fe/Fe3C electrocatalyst heat treated at 900°C showed superior characteristics than the case of carbonization at other temperatures, but showed a significant difference from platinum.

9, a graph showing the results of an Accelerated Degradation Test (ADT) for measuring the stability of the catalytically active part on the electrode catalyst according to another embodiment of the present invention, (ab) 0.1M potassium hydroxide electrolyte and ( cd) CV and LSV results are shown after running in 0.1M perchloric acid electrolyte.

When ADT is performed for 50,000 cycles, it can be seen that the active area of the catalyst is slightly reduced, but it can be confirmed that the loss is very small among catalysts other than noble metals.

Referring to FIG. 10 , a proton ion exchange membrane fuel cell (PEMFC) cell and an anion ion exchange membrane fuel cell (AEMFC) cell using a proton ion exchange membrane or an anion ion exchange membrane according to another embodiment of the present invention were 0 kPa (w/o bp) ), 50 kPa, and 250 kPa as a graph showing the voltage/current curve after pressurization, and the performance similar to that of the PEMFC/AEMFC battery using commercial Pt/C can be confirmed.

Although the present invention has been described in detail through specific examples, it is intended to describe the present invention in detail, and the present invention is not limited thereto. It is clear that the transformation or improvement is possible by the person.

All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will be made clear by the appended claims.

10: catalyst active part
11: transition metal core layer
12: carbon coating layer
20: carbon support
100: fuel cell
110: anode
120: air electrode
130: separator

Claims (15)

a catalytically active part exhibiting oxygen reduction activity; and
a carbon support part supporting the catalytically active part and allowing electrons to move;
including,
The catalytically active part,
a transition metal core layer in which a catalytic reaction occurs; and
a carbon coating layer formed by coating the outside of the transition metal core layer to improve stability;
including,
The carbon coating layer,
An electrocatalyst characterized in that it is doped with nitrogen and fluorine to improve oxygen reduction activity.
The method according to claim 1,
The transition metal core layer is ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), vanadium (V), tungsten (W), cobalt (Co) , from the group consisting of iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), cerium (Ce) and copper (Cu). Electrocatalyst comprising at least one or more elements.
The method according to claim 1,
The carbon coating layer,
Electrocatalyst comprising at least one element from the group consisting of nitrogen (N), fluorine (F), boron (B), and sulfur (S) in order to increase the activity of the transition metal core layer.
The method according to claim 1,
The catalytically active part,
Electrocatalyst, characterized in that it has a spherical, rod-shaped, linear or polyhedral shape so that oxygen reduction reaction occurs on the surface.
A polymer polymerization step of polymerizing a polymer composite by mixing a raw material including an aniline monomer, an aniline monomer including fluorine, a transition metal precursor exhibiting oxygen reduction activity, and an oxidizing agent;
a polymer drying step of drying the polymer composite;
a carbonization step of carbonizing the dried polymer composite by heat treatment;
an acid treatment step of acid-treating the electrode catalyst formed by carbonizing the polymer composite;
a heat treatment step of heat-treating the acid-treated electrode catalyst;
including,
In the polymer polymerization step,
An electrode catalyst manufacturing method for polymerizing the polymer composite through the oxidizing agent after the raw material is mechanically stirred.
6. The method of claim 5,
The transition metal precursor is
Ruthenium (Ru), Rhodium (Rh), Molybdenum (Mo), Osmium (Os), Iridium (Ir), Rhenium (Re), Vanadium (V), Tungsten (W), Cobalt (Co), Iron (Fe), Contains at least one element from the group consisting of selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), cerium (Ce), and copper (Cu) Electrocatalyst manufacturing method, characterized in that the compound.
6. The method of claim 5,
The oxidizing agent,
A method for producing an electrode catalyst comprising an acid selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, or a sulfate salt selected from at least one selected from ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, and potassium sulfate.
6. The method of claim 5,
In the polymer polymerization step,
An electrode catalyst manufacturing method, characterized in that the raw material is further mixed with a compound containing at least one element selected from the group consisting of nitrogen (N), fluorine (F), boron (B), and sulfur (S).
6. The method of claim 5,
In the polymer polymerization step,
An electrocatalyst manufacturing method, characterized in that the aniline monomer and the aniline monomer containing fluorine are composed of 1:1 volume ratio or more and 1:100 volume ratio and stirred at a rotation speed of 10 rpm or more and 400 rpm or less for 5 minutes or more and 100 hours or less.
6. The method of claim 5,
In the polymer polymerization step,
An electrocatalyst manufacturing method, characterized in that a solution containing the oxidizing agent in an amount of 0.1 M or more and 10 M or less is administered and stirred at a rotation speed of 10 rpm or more and 400 rpm or less for 5 minutes or more and 100 hours or less.
6. The method of claim 5,
In the polymer drying step,
An electrocatalyst manufacturing method, characterized in that drying is carried out at 10 degrees or more and 80 degrees or less for 5 hours or more and 24 hours or less so that the solvent contained in the polymer composite is removed.
6. The method of claim 5,
In the carbonization step,
An electrode catalyst manufacturing method, characterized in that the polymer composite is carbonized by heating it in a gas atmosphere containing at least one of nitrogen, hydrogen, or argon at a temperature of 300 degrees or more and 1000 degrees or less for 10 minutes or more and 24 hours or less.
6. The method of claim 5,
In the acid treatment step,
Electrode characterized in that it is supported in a solution containing at least one of hydrochloric acid, sulfuric acid, nitric acid and perchloric acid in an amount of 0.1 M or more and 1 M or less and acid-treated for 5 minutes or more and 24 hours or less so as to remove metal by-products from the carbonized electrode catalyst. Catalyst preparation method.
7. The method of claim 6,
In the heat treatment step,
An electrocatalyst manufacturing method, characterized in that the electrocatalyst is heated in a gas atmosphere containing at least one of nitrogen, hydrogen, or argon at a temperature of 300 degrees or more and 1000 degrees or less for 10 minutes or more and 24 hours or less.
A cathode comprising the electrocatalyst according to any one of claims 1 to 4;
anode to which fuel is supplied; and
a separation membrane provided between the cathode and the anode and through which ions are movable;
A fuel cell comprising a.

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