WO2015069068A1 - Catalyst for fuel cell and fuel cell comprising same - Google Patents

Abstract

The present disclosure provides a catalyst for a fuel cell and a fuel cell comprising the same.

Description

Catalyst for fuel cell and fuel cell comprising same

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2013-0135504 filed with the Korea Intellectual Property Office on November 8, 2013, the entire contents of which are incorporated herein.

The present specification relates to a fuel cell catalyst and a fuel cell including the same.

A fuel cell is a high efficiency, pollution-free power generation device that directly converts chemical energy of a reactant into electrical energy. It is currently used in household power plants or electric vehicles, and is also used in various fields such as industrial and military use. Fuel cells are classified into molten carbonate fuel cells, solid oxide fuel cells, alkali fuel cells, phosphoric acid fuel cells, polymer electrolyte fuel cells, and direct methanol fuel cells according to electrolytes, operating temperatures, and types of fuels. Among these fuel cells, the polymer electrolyte fuel cell has excellent energy conversion efficiency and high current density even at low temperature, so that development for various fields is being actively conducted.

The performance of a polymer electrolyte fuel cell is largely determined by the performance of a membrane positive electrode catalyst of a fuel cell, and platinum (Pt), which is one of its raw materials, has a great effect on the cost of a fuel cell because the price is very expensive. Accordingly, in order to improve fuel cell performance and reduce cost, many researches and developments of catalysts have been made.

In order to increase the activity of fuel cell catalysts, research has been conducted to manufacture platinum in nano size and to support platinum in high dispersion and high ratio on carbon having high surface area. In addition, research is being conducted using alloys with other metals to reduce the content of platinum, which accounts for most of the fuel cell cost.

[Preceding technical literature]

Korean Publication 10-2006-0082595

The present specification provides a fuel cell catalyst and a fuel cell including the same.

An exemplary embodiment of the present specification includes a carrier-metal nanoparticle complex in which metal nanoparticles including a first metal and a second metal are supported on a carrier, and the average particle diameter of the metal nanoparticles is 30 nm or less, and the carrier Provides a catalyst for a fuel cell that is doped with ceria.

Further, a solvent is formed by adding a solvent, a first metal salt providing a first metal ion in the solvent, a second metal salt providing an atomic group ion containing a second metal ion in the solvent, and at least one surfactant in the solvent. Doing; Adding a reducing agent to the solution to form metal nanoparticles; Doping ceria into the carrier; And supporting the metal nanoparticles on the carrier to form a carrier-metal nanoparticle complex, wherein the forming of the solution includes the surfactant forming a micelle and the first metal outside the micelle. It provides a method for producing a catalyst for a fuel cell comprising the surrounding ions and the second metal ion.

In addition, an exemplary embodiment of the present specification comprises the steps of doping the ceria to the carrier; A solvent is added to form a solution by adding a solvent, a first metal ion in the solvent or a first metal salt providing the first metal ion, a second metal salt providing a second metal ion in the solvent, and at least one surfactant. step; Adding and dispersing ceria-doped carrier to the solution; And adding a reducing agent to the solution to form a carrier-metal nanoparticle complex on which the metal nanoparticles are supported on the ceria-doped carrier, wherein the forming of the solution comprises the surfactant forming a micelle and It provides a method for producing a catalyst for a fuel cell comprising the first metal ion and the second metal ion surrounding the outside of the micelle.

In addition, the cathode; An anode disposed opposite the cathode; And an electrolyte membrane disposed between the cathode and the anode, wherein at least one of the cathode and the anode includes the fuel cell catalyst.

In addition, an exemplary embodiment of the present specification provides a fuel cell including the membrane electrode assembly.

A fuel cell catalyst according to an exemplary embodiment of the present specification exhibits better activity than carbon-supported platinum of the same mass even when a small amount of platinum (Pt) is used.

Fuel cell catalyst according to an exemplary embodiment of the present specification is excellent in oxygen reduction activity.

Fuel cell catalyst according to an exemplary embodiment of the present specification is excellent in durability. Specifically, the fuel cell catalyst according to one embodiment of the present specification may maintain excellent oxygen reduction activity even after long-term operation of the fuel cell.

Since the fuel cell catalyst according to one embodiment of the present specification can be manufactured at room temperature, the process can be simplified and the manufacturing cost can be reduced.

Since the catalyst for a fuel cell according to the exemplary embodiment of the present specification may use water as a solvent instead of an organic solvent, there is an advantage that a post-treatment process for treating an organic solvent is not required. Furthermore, the fuel cell catalyst according to one embodiment of the present specification can expect a cost reduction effect and an environmental pollution prevention effect.

1 is an exploded perspective view showing an embodiment of a fuel cell.

FIG. 2 is a schematic cross-sectional view of a membrane electrode assembly (MEA) constituting the fuel cell of FIG. 1.

3 illustrates an ORR reaction of a catalyst for a fuel cell according to an exemplary embodiment of the present specification.

4 and 5 are transmission electron microscope (TEM) images of a catalyst for a fuel cell prepared according to Example 1. FIG.

6 shows ORR measurement results according to Example 2 and Comparative Example 1. FIG.

In the present specification, when a part "contains" a certain component, this means that the component may further include other components, except for the case where there is no contrary description.

Hereinafter, this specification is demonstrated in detail.

An exemplary embodiment of the present specification includes a carrier-metal nanoparticle complex in which metal nanoparticles including a first metal and a second metal are supported on a carrier, and the average particle diameter of the metal nanoparticles is 30 nm or less, and the carrier Provides a catalyst for a fuel cell that is doped with ceria.

According to an exemplary embodiment of the present specification, the ceria may be 1% by weight or more and 10% by weight or less of the total mass of the carrier.

Within the content range of the ceria, the ceria may play a role of increasing the activity of the catalyst for the fuel cell. When the content of the ceria exceeds 10% by weight of the total mass of the carrier, the conductivity of the catalyst for the fuel cell and Activity may be lowered.

The ceria means cerium (Ce) oxide. The ceria may be prevented from deteriorating catalytic activity by the metal nanoparticles becoming oxides through a redox reaction by doping the ceria. In addition, the ceria also serves to store oxygen, thereby smoothly supplying oxygen to the adjacent metal nanoparticles, thereby increasing the activity of the catalyst for the fuel cell.

According to an exemplary embodiment of the present specification, the ceria may be represented by CeO _x (x = 1.5 to 2). Specifically, the ceria may be Ce ₂ O ₃ and / or CeO ₂ .

According to one embodiment of the present specification, the ceria may be a spherical particle, and the particle diameter of the ceria may be 5 nm or more and 20 nm or less.

According to one embodiment of the present specification, the ceria may be distributed on the surface of the carrier, and the ceria may be uniformly distributed on the surface of the carrier.

According to an exemplary embodiment of the present specification, the mass ratio of the metal nanoparticles and the carrier may be 1: 9 to 4: 6.

According to an exemplary embodiment of the present specification, the carrier may be a carbon-based material.

According to an exemplary embodiment of the present specification, the carbon-based material is carbon black, carbon nanotubes (CNT), graphite (Graphite), graphene (Graphene), activated carbon, porous carbon (Mesoporous Carbon), carbon fiber (Carbonfiber) and Carbon nano wire may be selected from the group consisting of.

According to one embodiment of the present specification, the average particle diameter of the metal nanoparticles may be 1 nm or more and 30 nm or less.

According to an exemplary embodiment of the present specification, the average particle diameter of the metal nanoparticles may be 1 nm or more and 20 nm or less.

According to an exemplary embodiment of the present specification, the average particle diameter of the metal nanoparticles may be 1 nm or more and 12 nm or less.

According to an exemplary embodiment of the present specification, the average particle diameter of the metal nanoparticles may be 1 nm or more and 10 nm or less.

According to one embodiment of the present specification, the average particle diameter of the metal nanoparticles may be 1 nm or more and 6 nm or less.

According to one embodiment of the present specification, the average particle diameter of the metal nanoparticles may be 30 nm or less, more specifically 20 nm or less, or 12 nm or less, or 10 nm or less. Alternatively, the average particle diameter of the metal nanoparticles may be 6 nm or less. The average particle diameter of the metal nanoparticles may be 1 nm or more. If the particle diameter of the metal nanoparticle is 30nm or less, the advantage that the nanoparticles can be used in various fields. Moreover, when the particle diameter of a metal nanoparticle is 20 nm or less, it is more preferable. In addition, when the particle size of the metal nanoparticles is 10nm or less, or 6nm or less, the surface area of the particles becomes wider, there is an advantage that the application possibility that can be used in various fields becomes larger. For example, if the metal nanoparticles formed in the particle size range is used as a catalyst, the efficiency can be significantly increased.

According to the exemplary embodiment of the present specification, the average particle diameter of the metal nanoparticles is measured for 200 or more metal nanoparticles using graphic software (MAC-View), and the average particle diameter is measured through the obtained statistical distribution. it means.

Hollow metal nanoparticles

According to an exemplary embodiment of the present specification, the metal nanoparticles are hollow cores; And a shell part including the first metal and the second metal. Specifically, according to one embodiment of the present specification, the metal nanoparticles may be hollow metal nanoparticles including a hollow core part and a shell part including the first metal and the second metal.

According to one embodiment of the present specification, at least two major peaks representing an atomic percentage of at least one of the first metal and the second metal may be present in the elemental analysis data of the metal nanoparticle.

In the graph showing the atomic percentage contained in the particles in the elemental analysis data of the particles, peaks mean points where the shape of the graph is sharp as the slope of the graph changes from a positive value to a negative value.

According to an exemplary embodiment of the present specification, the major peak refers to a peak located at the apex of each of the peaks of the connecting line connecting peaks among the peaks representing the atomic percentage contained in the particle in the elemental analysis data of the particle. Here, one peak located at the peak of each peak may be two or more having the same atomic percentage value.

According to an exemplary embodiment of the present specification, the major peak of each of the peaks having a height higher than the average value of the peaks of the peaks of the connecting line connecting the peaks among the peaks representing the atomic percentage contained in the particle in the elemental analysis data of the particles It means the peak located at the peak. Here, the average value of the peaks means the average value of all the peaks representing the atomic percentages.

According to an exemplary embodiment of the present specification, the major peak of the peak having the first or second highest height among the peaks of the connecting line connecting the peaks among the peaks representing the atomic percentage contained in the particle in the elemental analysis data of the particle. It means the peak located at the peak.

According to the exemplary embodiment of the present specification, when the particle diameter of the metal nanoparticle is 100%, at least one major peak representing the atomic percentage of the first metal exists in an area of 0% to 30% from one end point of the particle diameter. And at least one other major peak representing the atomic percentage of the first metal in the region of 0% to 30% from the other end point of the particle diameter.

According to one embodiment of the present specification, when the particle diameter of the metal nanoparticle is 100%, at least one major peak indicating an atomic percentage of the second metal exists in an area of 0% to 30% from one end point of the particle diameter. And at least one other major peak representing the atomic percentage of the second metal in the region of 0% to 30% from the other end point of the particle diameter.

In this case, the particle diameter of the metal nanoparticle means a starting point or one end point of the graph to which the peak of the first metal is connected to the other end point, and the starting point or the end point is a point at which the graph of the first metal peak is connected; Alternatively, it means a point where the vertical value of the graph in which the peak of the first metal is connected becomes zero.

According to an exemplary embodiment of the present specification, there may be at least two major peaks representing the atomic percentage of the second metal. In this case, when the particle diameter of the metal nanoparticle is 100%, at least one major peak representing the atomic percentage of the second metal exists in an area of 0% to 30% from one end point of the particle size, and from the other end point of the particle size. There may be another at least one major peak representing the atomic percentage of the second metal in the region of 0% to 30%.

In addition, the particle diameter of the metal nanoparticle means a starting point or one end point of the graph to which the peak of the second metal is connected to the other end point, and the starting point or the end point is the point where the graph to which the peak of the second metal is connected is started or It means the point where the vertical value of the graph connected with the peak becomes 0.

According to an exemplary embodiment of the present specification, a plurality of peaks representing the atomic percentage of the first metal or the second metal may be present in all regions of the particle diameter.

According to one embodiment of the present specification, a hollow core part; And a shell portion including the first metal and the second metal, wherein at least two major peaks representing the atomic percentage of the first metal are present in the elemental analysis data of the particle, and representing the atomic percentage of the second metal. Peaks may provide a plurality of metal nanoparticles present in the entire region of the particle diameter.

According to one embodiment of the present specification, a hollow core part; And a shell portion including the first metal and the second metal, wherein at least two major peaks representing the atomic percentage of the second metal are present in the elemental analysis data of the particle, and representing the atomic percentage of the first metal. Peaks may provide a plurality of metal nanoparticles present in the entire region of the particle diameter.

According to one embodiment of the present specification, a hollow core part; And a shell portion including the first metal and the second metal, wherein at least two major peaks representing the atomic percentage of the first metal are present in the elemental analysis data of the particle, and representing the atomic percentage of the second metal. It is possible to provide metal nanoparticles in which at least two major peaks are present.

Cross-sectional elemental analysis data of the particles may be obtained using an energy dispersive spectrometer (EDS). Specifically, the cross-sectional elemental analysis data is to determine which element is measured in the two-dimensional region when the particle is viewed through the above. That is, in the case of the metal nanoparticles, the shell part can be observed in the form of a major peak because the elements are densely distributed than the region where the hollow is located. Furthermore, when the amount of the element is relatively small, it can be observed as a plurality of peaks in the entire region.

In the present specification, hollow means that the core portion of the metal nanoparticle is empty. In addition, the hollow may be used as the same meaning as the hollow core. The hollow includes the terms hollow, hole, void, porous.

According to one embodiment of the present specification, the hollow may include a space in which no internal material is present at 50 vol% or more, specifically 70 vol% or more, more specifically 80 vol% or more. Alternatively, at least 50% by volume, specifically 70% by volume, more specifically 80% by volume may include an empty space. Or a space having an internal porosity of at least 50% by volume, specifically at least 70% by volume, more specifically at least 80% by volume.

According to one embodiment of the present specification, the volume of the hollow core part may be 50 vol% or more, specifically 70 vol% or more, more specifically 80 vol% or more of the total volume of the metal nanoparticles. According to an exemplary embodiment of the present specification, the volume of the hollow core portion may be less than 100% by volume of the total volume of the metal nanoparticles. In addition, according to one embodiment of the present specification, the volume of the hollow core portion may be 90% by volume or less of the total volume of the metal nanoparticles.

According to one embodiment of the present specification, the shell portion of the metal nanoparticle may be formed of a metal including a first metal and a second metal. That is, the shell portion of the metal nanoparticle of the present invention may be formed of a metal rather than a metal oxide.

According to an exemplary embodiment of the present specification, the shell portion is present in the front of the outer hollow, it may be present in the form surrounding the hollow. Specifically, according to one embodiment of the present specification, the shell portion may be formed on the entire hollow outer surface. That is, the shell portion may form the form of the metal nanoparticles.

According to one embodiment of the present specification, the metal nanoparticles may have a spherical shape. In this case, the shell portion may have a spherical shape including a hollow core.

The spherical shape does not mean only a perfect spherical shape, but may include an approximately spherical shape. For example, the metal nanoparticle may not have a spherical outer surface, and the radius of curvature of the metal nanoparticle may not be constant.

According to an exemplary embodiment of the present specification, the shell portion may be a shell of a single layer, or may be a shell of two or more layers.

According to one embodiment of the present specification, the shell part may be formed by mixing the first metal and the second metal. Specifically, when the shell portion is a single layer, the first metal and the second metal may be present in a mixed form. At this time, it may be mixed uniformly or heterogeneously.

According to an exemplary embodiment of the present specification, the shell portion includes a first shell made of the first metal; And a second shell made of the second metal.

Alternatively, according to the exemplary embodiment of the present specification, the shell part may include a first shell including a first metal; And it may include a plurality of shells including a second shell comprising a second metal.

According to an exemplary embodiment of the present specification, when the shell portion is a single layer, the first metal and the second metal may be present in a mixed form. At this time, it may be mixed uniformly or heterogeneously.

According to an exemplary embodiment of the present specification, the atomic percentage ratio of the first metal and the second metal of the shell portion may be 1: 5 to 10: 1.

According to one embodiment of the present specification, when the shell portion is a single layer, the ratio of the first metal in the shell may exist in a gradation state. The proportion of the second metal may be present at a constant rate in the shell and the first metal may be present at a rate in the form of a gradient.

For example, based on the cross section of the shell, the ratio of the first metal at the center may be the highest, and the ratio of the first metal may be lowered toward both ends of the shell. That is, the ratio of the first metal may increase from the portion adjacent to the hollow core toward the center of the shell, and the ratio of the first metal may decrease from the center of the shell toward the outer edge of the shell. In this case, a point where the ratio of the first metal is the highest may exist at the center of the shell.

As another example, the portion of the shell in contact with the hollow core may be present at least 50%, or at least 70% by volume of the first metal, and the surface portion of the shell in contact with the outside may be at least 50%, or 70% by volume of the second metal. It may be present in more than%.

Alternatively, the shell may be a first shell or a second shell separately formed with different mixing ratios of the first metal and the second metal, respectively. In this case, the atomic percentage ratio of the first metal to the second metal in each shell may be 1: 5 to 10: 1.

According to one embodiment of the present specification, when the shell portion is two or more layers, each shell may include only the first metal or the second metal. For example, the metal nanoparticles may comprise a hollow core; One or more first shells comprising a first metal; And one or more second shells comprising a second metal.

According to one embodiment of the present specification, the first shell may be present on the front surface of the hollow exterior.

The second shell may be present in at least one region of the outer surface of the first shell and may exist in a form surrounding the front surface of the outer surface of the first shell. If the second shell is present in some region of the outer surface of the first shell it may be present in the form of discontinuous faces.

According to the exemplary embodiment of the present specification, the metal nanoparticle may include a hollow core, a first shell including a first metal formed on the entire outer surface of the hollow core, and a second metal formed on the entire outer surface of the first shell. It may include a second shell including. Alternatively, according to one embodiment of the present specification, the metal nanoparticle may include a single layer shell including the first metal and the second metal formed on the entire outer surface of the hollow core. In this case, the hollow core may include a surfactant having a positive charge.

According to an exemplary embodiment of the present specification, the thickness of the shell portion in the metal nanoparticles may be more than 0nm 5nm or less, more specifically more than 0nm 3nm or less.

For example, the average particle diameter of the metal nanoparticles may be 30 nm or less, the thickness of the shell portion may be greater than 0 nm and 5 nm or less, and more specifically, the average particle diameter of the metal nanoparticles may be 20 nm or less or 10 nm or less, and the thickness of the shell portion is 0 nm. Greater than or equal to 3 nm. According to one embodiment of the present specification, the hollow particle diameter of the metal nanoparticle may be 1 nm or more and 10 nm or less, specifically 1 nm or more and 4 nm or less. In addition, the thickness of each shell may be 0.25 nm or more and 5 nm or less, specifically 0.25 nm or more and 3 nm or less. The shell portion may be a shell formed by mixing the first metal and the second metal, or may be a plurality of shells including a first shell and a second shell, each having a different mixing ratio of the first metal and the second metal. Alternatively, the plurality of shells may include a first shell including only the first metal and a second shell including only the second metal.

According to an exemplary embodiment of the present specification, the hollow nanoparticles may include a surfactant inside the hollow core.

Hollow metal nanoparticles containing a cavity

According to an exemplary embodiment of the present specification, the metal nanoparticles are hollow cores; A shell part including a first metal and a second metal; And a cavity extending from an outer surface of the shell portion to the hollow core in one or two or more regions of the shell portion. Specifically, the metal nanoparticles are hollow cores; A shell part including a first metal and a second metal; And hollow metal nanoparticles including a cavity extending from an outer surface of the shell portion to the hollow core in at least one region of the shell portion.

According to an exemplary embodiment of the present specification, the metal nanoparticle may include one cavity.

According to an exemplary embodiment of the present specification, the volume of the hollow core portion may be at least 50% by volume of the total volume of the hollow metal nanoparticles.

According to one embodiment of the present specification, the metal nanoparticles may have a spherical shape. In this case, the shell portion may have a spherical shape including a hollow core.

The spherical shape does not mean only a perfect spherical shape, but may include an approximately spherical shape. For example, the metal nanoparticle may not have a spherical outer surface, and the radius of curvature of the metal nanoparticle may not be constant.

According to the exemplary embodiment of the present specification, the hollow metal nanoparticle including the cavity may include at least one region of the shell portion of the hollow metal nanoparticle described above including the cavity. Therefore, the details of the hollow core portion, shell portion and particle diameter of the hollow metal nanoparticle including the cavity may be as described above.

Metal Nanoparticles Including Tunnels

According to an exemplary embodiment of the present specification, the metal nanoparticles may include one or more tunnels continuous from an outer surface. Specifically, according to one embodiment of the present specification, the metal nanoparticles may be metal nanoparticles including the tunnel as metal nanoparticles that do not include a hollow therein.

According to one embodiment of the present specification, the tunnel may mean an empty space continuous from one region of the outer surface of the metal nanoparticle. The tunnel of the present specification may be formed in the form of a continuous empty space from one or more regions of the outer surface of the metal nanoparticles to one region inside the metal nanoparticles. In addition, the cavity of the present specification may be formed in the form of a tunnel penetrating the metal nanoparticle from one or two or more regions of the outer surface of the metal nanoparticle. The tunnel form may be a straight line, a continuous form of a curve or a straight line, it may be a continuous form of a mixture of curves and straight lines.

The tunnel may serve to utilize the inner surface area of the metal nanoparticles. Specifically, when the metal nanoparticles are used for the purpose of a catalyst or the like, the tunnel may serve to increase the surface area that can be in contact with the reactants. Therefore, the tunnel may serve to exhibit high activity of the metal nanoparticles.

Specifically, the metal nanoparticles of the present disclosure may increase the surface area by 20% to 50% compared to the metal nanoparticles in the absence of the tunnel due to the tunnel.

According to an exemplary embodiment of the present specification, the diameter of the tunnel may be 5% or more and 30% or less of the metal nanoparticle particle diameter.

When the diameter of the tunnel is less than 5% of the particle diameter of the metal nanoparticles, the activity of the metal nanoparticles may not be sufficiently exhibited. In addition, when the diameter of the tunnel exceeds 30% of the particle size of the metal nanoparticles, the shape of the metal nanoparticles may not be maintained. Therefore, when the diameter of the tunnel is 5% or more and 30% or less of the particle diameter of the metal nanoparticles, the contact area with the reactant through the tunnel may be sufficiently widened.

According to one embodiment of the present specification, any one or more of the tunnels may pass through the metal nanoparticles.

According to one embodiment of the present specification, the tunnel may be continuous to one inner region of the metal nanoparticle.

According to one embodiment of the present specification, the tunnel may be cylindrical. Alternatively, the cavity may be bowl-shaped.

The cylindrical in this specification does not necessarily mean a perfect cylinder, but means that the approximate shape is cylindrical.

The bowl type of the present specification may be a hemispherical shape or a calabash shape.

The diameter of the cylindrical tunnel of the present specification can be kept constant. Specifically, the cylindrical tunnel of the present specification may be formed continuously with a difference in diameter of about 10%.

According to an exemplary embodiment of the present specification, the metal nanoparticles may include an alloy of the first metal and the second metal. Specifically, the metal nanoparticles of the present specification may be formed of an alloy of the first metal and the second metal except for the cavity.

According to one embodiment of the present specification, the metal nanoparticles may be uniformly mixed with the first metal and the second metal.

According to one embodiment of the present specification, the metal nanoparticles may have a spherical shape. The spherical shape is as described above.

According to an exemplary embodiment of the present specification, the content of the particle diameter of the metal nanoparticle including the tunnel may be as described above.

Bowl-type Metal Nanoparticles

According to the exemplary embodiment of the present specification, the metal nanoparticle may include one or more bowl-type particles including the first metal and the second metal. Specifically, according to one embodiment of the present specification, the metal nanoparticles may be bowl-type metal nanoparticles.

The bowl type in the present specification may mean that the curved area on the cross section includes at least one. Alternatively, the bowl type may mean that a curved area and a straight area are mixed on the cross section. Alternatively, the bowl type may be a hemispherical shape, and the hemispherical shape may be a shape in which one region of the sphere is removed, not necessarily divided to pass through the center of the sphere. Furthermore, the phrase does not mean only a perfect sphere, but may include an approximately spherical shape. For example, the outer surface of the sphere may not be flat and the radius of curvature of the sphere may not be constant. Alternatively, the bowl-type particle of the present specification may mean that 30% to 70% of the hollow nanoparticles are not continuously formed.

According to the exemplary embodiment of the present specification, the metal nanoparticle may be composed of one bowl-type particle.

According to the exemplary embodiment of the present specification, the metal nanoparticle may have a form in which two bowl-type particles partially contact each other.

The metal nanoparticles in the form of the two bowl-type particles partially contacted with each other may be in the form of a portion of the hollow nanoparticles split.

According to the exemplary embodiment of the present specification, an area in which the bowl-type particle partially contacts may include an area in which the inclination of the tangent line is reversed.

According to one embodiment of the present specification, the particle diameter of the bowl-type particle may be 1 nm or more and 30 nm or less. Specifically, the particle diameter of the bowl-type particles may be 1 nm or more and 20 nm or less, and more specifically, the particle size of the bowl-type particles may be 3 nm or more and 10 nm or less.

When the particle diameter of the metal nanoparticles is 30 nm or less, there is an advantage that the nanoparticles can be used in various fields. Moreover, when the particle diameter of a metal nanoparticle is 20 nm or less, it is more preferable. Furthermore, when the thickness of the metal nanoparticles is 10 nm or less, since the surface area of the particles becomes wider, there is an advantage in that the application possibility that can be used in various fields becomes larger. For example, when hollow metal nanoparticles formed in the particle size range are used as a catalyst, the efficiency can be significantly increased.

The particle diameter of the bowl-type particle of the present specification may mean a straight longest distance from one terminal region to the other region of the bowl-type particle. Alternatively, the particle diameter of the bowl-type particle may mean a particle diameter of an imaginary sphere including the bowl-type particle. According to one embodiment of the present specification, the bowl-type particle may be a single layer. In this case, the single layer may include both the first metal and the second metal.

According to the exemplary embodiment of the present specification, when the bowl-type particle is a single layer, the first metal and the second metal may be present in a mixed form. Further, when the bowl-type particle is a single layer, the first metal and the second metal may be mixed uniformly or non-uniformly.

According to one embodiment of the present specification, the bowl-type particle may be two or more layers. Specifically, according to one embodiment of the present specification, when the bowl-type particle has two or more layers, a first layer including the first metal; And a second layer including the second metal.

According to the exemplary embodiment of the present specification, the first layer may include the first metal and may not include the second metal. In addition, the second layer may include the second metal and may not include the first metal.

In addition, according to one embodiment of the present specification, the first layer may have a higher content of the first metal than the content of the second metal. In addition, the second layer may have a higher content of the second metal than that of the first metal.

According to one embodiment of the present specification, the bowl-type particle may include a first layer having a content of the first metal higher than that of the second metal; And a second layer having a higher content of the second metal than that of the first metal.

Specifically, according to one embodiment of the present specification, the content of the first metal in the first layer is the highest in the region farthest away from the second layer, and the closer to the second layer, the first The content of metal can be gradually reduced. In addition, the content of the second metal in the first layer may increase as the distance from the second layer.

Further, according to one embodiment of the present specification, the content of the second metal in the second layer is the highest in the region farthest away from the first layer, and the closer to the first layer, the second metal The content of can gradually become smaller. In addition, the content of the second metal in the second layer may increase as the distance from the first layer.

Specifically, the metal nanoparticles may be present in a state where the first metal and the second metal are gradated, and the first metal is 50 vol% or more in the region farthest away from the second layer in the first layer, Or 70 vol% or more, and the second metal may be present in the region farthest away from the first layer in an amount of 50 vol% or more, or 70 vol% or more.

According to the exemplary embodiment of the present specification, the thickness of the bowl-type particle may be greater than 0 nm and 5 nm or less. Specifically, the thickness of the bowl-type particles may be more than 0 nm 3 nm or less.

In the present specification, the thickness of the bowl-type particle may mean the thickness of the metal layer forming the bowl-type particle.

According to an exemplary embodiment of the present specification, the first metal and the second metal are different from each other, and in the group consisting of a metal, a metalloid, a lanthanum group metal, and an actinium group metal belonging to groups 3 to 15 of the periodic table, respectively It may be selected.

Specifically, according to one embodiment of the present specification, the first metal and the second metal are different from each other, and platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), and osmium (Os), respectively. ), Iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi) ), Tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), silver (Ag) and copper (Cu).

According to an exemplary embodiment of the present specification, any one of the first metal and the second metal is platinum (Pt), and the other one is nickel (Ni), cobalt (Co), iron (Fe), copper (Cu ) Or palladium (Pd). Specifically, according to one embodiment of the present specification, one of the first metal and the second metal may be platinum (Pt), and the other may be nickel (Ni).

According to one embodiment of the present specification, the particle diameter of the plurality of metal nanoparticles may be in the range of 80% to 120% of the average particle diameter of the metal nanoparticles. Specifically, the particle diameter of the metal nanoparticles may be in the range of 90% to 110% of the average particle diameter of the metal nanoparticles. If it is out of the above range, since the size of the metal nanoparticles becomes entirely non-uniform, it may be difficult to secure the specific physical properties required by the metal nanoparticles. For example, when metal nanoparticles outside the range of 80% to 120% of the average particle diameter of the metal nanoparticles are used as the catalyst, the activity of the catalyst may be somewhat insufficient.

According to one embodiment of the present specification, the shape of the metal nanoparticle may be a shape including one or more spherical or bowl-type particles.

Further, a solvent is formed by adding a solvent, a first metal salt providing a first metal ion in the solvent, a second metal salt providing an atomic group ion containing a second metal ion in the solvent, and at least one surfactant in the solvent. Doing; Adding a reducing agent to the solution to form metal nanoparticles; Doping ceria into the carrier; And supporting the metal nanoparticles on the carrier to form a carrier-metal nanoparticle complex, wherein the forming of the solution includes the surfactant forming a micelle and the first metal outside the micelle. It provides a method for producing a catalyst for a fuel cell comprising the surrounding ions and the second metal ion.

According to an exemplary embodiment of the present specification, the forming of the carrier-metal nanoparticle complex may include adding a carrier after forming the metal nanoparticle.

In addition, an exemplary embodiment of the present specification comprises the steps of doping the ceria to the carrier; A solvent is added to form a solution by adding a solvent, a first metal ion in the solvent or a first metal salt providing the first metal ion, a second metal salt providing a second metal ion in the solvent, and at least one surfactant. step; Adding and dispersing ceria-doped carrier to the solution; And adding a reducing agent to the solution to form a carrier-metal nanoparticle complex on which the metal nanoparticles are supported on the ceria-doped carrier, wherein the forming of the solution comprises the surfactant forming a micelle and It provides a method for producing a catalyst for a fuel cell comprising the first metal ion and the second metal ion surrounding the outside of the micelle.

Specifically, the forming of the carrier-metal nanoparticle complex may include adding the carrier to the solution before adding the reducing agent. That is, according to the fuel cell catalyst manufacturing method according to one embodiment of the present specification, the metal nanoparticles may be prepared on a carrier. In this case, since the carrier is added in the intermediate step of the manufacturing method, the adhesion between the carrier and the manufactured hollow metal nanoparticles is improved, so that the stability of the hollow metal nanoparticles is excellent.

According to the fuel cell catalyst manufacturing method according to an exemplary embodiment of the present specification, there is also an advantage that the dispersion degree of the hollow metal nanoparticles on the carrier is excellent. The higher the dispersion degree, the more active points can participate in the reaction, the better the reactivity is. In addition, since the interaction between the metal nanoparticles and the carrier is improved, durability may be improved.

According to an exemplary embodiment of the present specification, the doping the ceria on the carrier may be to doping the ceria on the carrier using a cerium (Ce) precursor. According to an exemplary embodiment of the present specification, the cerium precursor is cerium nitrate (Ce (NO ₃ ) ₂ ), cerium chloride, cerium carbonate and / or cerium acetate And so on.

According to an exemplary embodiment of the present specification, the step of doping the ceria in the carrier is a precipitate of the cerium precursor using a material such as ammonium carbonate, urea (Narea), NaOH and the like, and then heat-treated the ceria-doped carrier It may be to form.

According to one embodiment of the present specification, the surfactant may include one or two selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants. have.

According to one embodiment of the present specification, the surfactant may be one kind of surfactant, and may be a cationic surfactant or an anionic surfactant.

According to an exemplary embodiment of the present specification, the forming of the solution may include adding the first metal salt, the second metal salt, and a surfactant to a solvent.

According to an exemplary embodiment of the present specification, the first metal ion may be in a form surrounding the outer surface of the surfactant forming the micelle. In addition, the second metal ion may have a shape surrounding the first metal ion. The first metal ion and the second metal ion may form a shell part including the first metal and the second metal, respectively, by a reducing agent.

According to an exemplary embodiment of the present specification, the surfactant may form a micelle in the solution. The charge of the surfactant may be classified according to the kind of the charge on the outer surface of the micelle. That is, when the charge on the outer surface of the micelle is anionic, the surfactant forming the micelle may be an anionic surfactant. In addition, when the charge on the outer surface of the micelle is cationic, the surfactant forming the micelle may be a cationic surfactant.

When the surfactant is an anionic surfactant, since the outer surface of the surfactant forming the micelle is anionic, it may be surrounded by a first metal ion having a cation. Furthermore, the first metal salt may be surrounded by a second metal ion having an anion.

According to the exemplary embodiment of the present specification, the region in which the anionic surfactant forms the micelle is such that the first metal ion bearing the cation and the second metal ion bearing the anion do not exist, thereby forming a hollow. Can be. That is, when the first metal ion and the second metal ion are formed as a shell part including the first metal and the second metal by a reducing agent, the region forming the micelle may be a hollow core not containing metal. .

When the surfactant is a cationic surfactant, since the outer surface of the surfactant forming the micelle is cationic, it may be surrounded by a first metal ion having an anion. Furthermore, the first metal ion may be surrounded by a second metal ion carrying a cation.

According to one embodiment of the present specification, the region in which the cationic surfactant forms the micelle is such that the first metal ion bearing the anion and the second metal ion bearing the cation do not exist, thereby forming a hollow. Can be. That is, when the first metal ion and the second metal ion are formed as a shell part including the first metal and the second metal by a reducing agent, the region forming the micelle may be a hollow core not containing metal. .

According to one embodiment of the present specification, in the forming of the solution, when the surfactant is one cationic surfactant or one anionic surfactant, hollow metal nanoparticles including a hollow core part are formed. Can be.

According to one embodiment of the present specification, the surfactant may include two types of surfactants, a first surfactant and a second surfactant. Specifically, according to one embodiment of the present specification, the first surfactant may form a micelle in the solvent, and the second surfactant may form a micelle in the solvent together with the first surfactant.

According to an exemplary embodiment of the present specification, when the surfactant includes the first surfactant and the second surfactant, a cavity may be formed in one or two or more regions of the shell portion.

According to an exemplary embodiment of the present specification, the concentration of the second surfactant; Chain length; The size of the outer end; Alternatively, by adjusting the type of charge, a cavity may be formed in one or two or more regions of the shell portion.

According to one embodiment of the present specification, the first surfactant may serve to form a micelle in a solution so that the first metal ion and the second metal ion form a shell portion, and the second surfactant It may serve to form a cavity of the metal nanoparticles.

According to one embodiment of the present specification, the forming of the solution may include adjusting the size or number of the cavities by varying concentrations of the first and second surfactants. Specifically, according to one embodiment of the present specification, the molar concentration of the second surfactant may be 0.01 to 0.05 times the molar concentration of the first surfactant. That is, the molar concentration of the second surfactant may be 1/100 to 1/20 times the molar concentration of the first surfactant. Specifically, the molar concentration of the second surfactant may be 1/30 to 1/10 of the molar concentration of the first surfactant.

According to one embodiment of the present specification, in the forming of the solution, the first surfactant and the second surfactant may form micelles according to the concentration ratio. By adjusting the molar concentration ratios of the first and second surfactants, the cavity size or the number of the cavity of the metal nanoparticles may be adjusted. Furthermore, the metal nanoparticles including one or more bowl-type particles may be prepared by continuously forming the cavity.

Further, according to one embodiment of the present specification, the forming of the solution may include adjusting the size of the cavity by adjusting the size of the outer end of the second surfactant.

In addition, according to one embodiment of the present specification, the forming of the solution may include adjusting the chain length of the second surfactant differently from the chain length of the first surfactant to form a cavity in the second surfactant region. It may include the step.

According to an exemplary embodiment of the present specification, the chain length of the second surfactant may be 0.5 to 2 times the chain length of the first surfactant. Specifically, the chain length may be determined by the number of carbons.

According to an exemplary embodiment of the present specification, by varying the chain length of the second surfactant and the chain length of the first surfactant, the metal ion bonded to the outer end of the second surfactant is a shell of the metal nanoparticles It is possible to prevent the formation of wealth.

Further, according to one embodiment of the present specification, the forming of the solution may include controlling the charge of the second surfactant differently from the charge of the first surfactant to form a cavity.

According to an exemplary embodiment of the present specification, the first metal ion of the charge opposite to the first and second surfactant may be located at the outer ends of the first and second surfactant forming the micelle in the solvent. The second metal ion may be disposed on an outer surface of the second metal ion opposite to the charge of the first metal ion.

According to the exemplary embodiment of the present specification, the first metal ion and the second metal ion formed at the outer end of the first surfactant may form a shell portion of the metal nanoparticle, and the outer side of the second surfactant The first metal ion and the second metal ion positioned at the end may not form the shell and may form a cavity.

According to one embodiment of the present specification, when the first surfactant is an anionic surfactant, in the forming of the solution, the first surfactant forms a micelle, and the micelle is a cation of a first metal ion. Can be enclosed. Furthermore, an anion including a second metal ion may surround the cation. Further, in the step of forming a metal nanoparticle by adding a reducing agent, the cation surrounding the micelles may form a first shell, the anion surrounding the cation may form a second shell.

According to one embodiment of the present specification, when the first surfactant is a cationic surfactant, in the forming of the solution, the first surfactant forms a micelle, and the micelle includes a first metal ion. It may be surrounded by anions. Furthermore, a second metal ion of the cation may surround the anion. In addition, in the step of forming a metal nanoparticle by adding a reducing agent, the anion surrounding the micelle may form a first shell, the cation surrounding the anion may form a second shell.

According to one embodiment of the present specification, the forming of the metal nanoparticles may include forming the first and second surfactant regions forming the micelle in a hollow manner.

According to one embodiment of the present specification, the forming of the metal nanoparticles may include filling the first and second surfactant regions forming the micelle with metal. Specifically, when the chain length of the second surfactant is longer or shorter than the length of the first surfactant forming the micelle, the first metal ion and the second metal ion may be filled in the micelle.

According to one embodiment of the present specification, when the insides of the first and second surfactants are filled with metal, metal nanoparticles including one or two or more cavities may be manufactured without hollowing.

According to one embodiment of the present specification, both the first surfactant and the second surfactant may be cationic surfactants.

According to an exemplary embodiment of the present specification, both the first surfactant and the second surfactant may be an anionic surfactant.

According to one embodiment of the present specification, when the first and second surfactants have the same charge, micelles may be formed by making the chain length of the second surfactant different from the chain length of the first surfactant. .

Specifically, due to the difference in the chain length of the second surfactant, the first and second metal ions located at the outer end of the second surfactant are positioned at the outer ends of the first surfactant. It is not adjacent to the ions and no shell portion is formed.

According to one embodiment of the present specification, any one of the first surfactant and the second surfactant may be an anionic surfactant, and the other may be a cationic surfactant. That is, in one embodiment of the present specification, the first and second surfactants may have different charges.

According to one embodiment of the present specification, when the first and second surfactants have different charges, the length of the chain may be different to form a cavity of the metal nanoparticle. In this case, the principle in which the cavities are formed is the same as when the aforementioned first and second surfactants have the same charge.

According to one embodiment of the present specification, when the first and second surfactants have different charges, even if the chains of the first and second surfactants have the same length, they may form a cavity of the metal nanoparticles. have. In this case, the outer end of the first surfactant adjacent to the second end of the second surfactant of the micelle is charged with each other to form a neutral, the metal ion is not located. Therefore, the portion where the metal ion is not located does not form the shell portion, thereby forming the cavity of the metal nanoparticles.

According to one embodiment of the present specification, the first surfactant may be an anionic surfactant or a cationic surfactant, and the second surfactant may be a nonionic surfactant.

According to the exemplary embodiment of the present specification, when the second surfactant is a nonionic surfactant, since the metal ion is not positioned at the outer end of the second surfactant, the cavity of the metal nanoparticles may be formed. Therefore, when the second surfactant is nonionic, it is possible to form a cavity of the metal nanoparticle even when the length of the chain is the same or different from the first surfactant.

According to one embodiment of the present specification, the first surfactant may be an anionic surfactant or a cationic surfactant, and the second surfactant may be a zwitterionic surfactant.

According to one embodiment of the present specification, when the second surfactant is an amphoteric ionic surfactant, since the metal ion is not located at the outer end of the second surfactant, the cavity of the metal nanoparticles may be formed. . Therefore, when the second surfactant is zwitterionic, it is possible to form a cavity of the metal nanoparticle even when the length of the chain is the same or different from the first surfactant.

According to one embodiment of the present specification, when the solution is formed by including two different kinds of surfactants, the hollow nanoparticles including the pores, the metal nanoparticles including the tunnel, or the bowl-type particles include one or more. Metal nanoparticles can be prepared.

Forming the metal nanoparticles according to the exemplary embodiment of the present specification has an advantage that the reduction potential between the first metal and the second metal is not considered because the reduction potential is not used. Since a charge between metal ions is used, there is an advantage that the method is simple compared to the conventional manufacturing method, and mass production is easy.

According to one embodiment of the present specification, the first metal salt is not particularly limited as long as it can be ionized in a solution to provide metal ions of the first metal. The first metal salt may comprise the first metal. Here, the first metal may be different from the second metal.

According to one embodiment of the present specification, the second metal salt is not particularly limited as long as it can be ionized in a solution to provide metal ions of the second metal. The second metal salt may comprise a second metal. Here, the second metal may be different from the first metal.

According to an exemplary embodiment of the present specification, the first metal salt and the second metal salt are nitrates (Nitrate, NO ^{3 −} ), chlorides (Chloride, Cl ⁻ ), and bromide (Bomide, Br) of the first metal and the second metal, respectively. ^-), iodide (iodide, I ^-), a halide (halide), hydroxide (hydroxide, such as ^OH-number of days) or sulfur oxide (sulfate, SO ^4-), but is not limited to this.

According to an exemplary embodiment of the present specification, the molar ratio of the first metal salt and the second metal salt may be 1: 1 to 10: 1, specifically 2: 1 to 5: 1. When the number of moles of the first metal salt is less than the number of moles of the second metal salt, it is difficult for the first metal to form the first shell including the hollow. In addition, when the number of moles of the first metal salt exceeds 10 times the number of moles of the second metal salt, it is difficult to form the second shell in which the second metal salt surrounds the first shell.

According to an exemplary embodiment of the present specification, the solvent may be a solvent including water. Specifically, in one embodiment of the present invention, the solvent dissolves the first metal salt and the second metal salt, and may be water or a mixture of water and an alcohol of C1 to C6, and specifically, may be water.

Since the method for preparing a catalyst for a fuel cell of the present specification may not use an organic solvent as a solvent, the post-treatment process of treating an organic solvent in a manufacturing process is not necessary, and thus, there is a cost saving effect and an environmental pollution prevention effect. .

The anionic surfactants herein are ammonium lauryl sulfate, sodium 1-heptanesulfonate, sodium hexanesulfonate, Sodium dodecyl sulfate, triethanol ammonium dodecylbenzene sulfate, potassium laurate, triethanolamine stearate, lithium dodecyl sulfate, sodium lauryl sulfate, alkyl polyoxyethylene sulfate, sodium alginate, dioctyl sodium sulfosuccinate, phosphatidyl Glycerol, phosphatidyl inositol, phosphatidylserine, phosphatidic acid and salts thereof, glyceryl esters, sodium carboxymethylcellulose, bile acids and salts thereof, cholic acid, deoxycholic acid, glycocholic acid, taurocholic acid, glycodeoxycholic acid, alkyl sulfonates , Aryl sulfonates, alkyl phosphates, alkyl phosphonates, stearic acid and salts thereof, calcium stearate, phosphate, carboxymethylcellulose sodium, dioctylsulfosuccinate, dialkylesters of sodium sulfosuccinic acid, phospholipids and calcium carboxymethylcellulose Selected from the group consisting of It may be. However, the present invention is not limited thereto.

The cationic surfactants herein are quaternary ammonium compounds, benzalkonium chloride, cetyltrimethylammonium bromide, chitosan, lauryldimethylbenzylammonium chloride, acyl carnitine hydrochloride, alkylpyridinium halides, cetyl pyridinium chloride , Cationic lipids, polymethylmethacrylate trimethylammonium bromide, sulfonium compounds, polyvinylpyrrolidone-2-dimethylaminoethyl methacrylate dimethyl sulfate, hexadecyltrimethyl ammonium bromide, phosphonium compounds, benzyl-di (2 -Chloroethyl) ethylammonium bromide, coconut trimethyl ammonium chloride, coconut trimethyl ammonium bromide, coconut methyl dihydroxyethyl ammonium chloride, coconut methyl dihydroxyethyl ammonium bromide, decyl triethyl ammonium chloride, decyl dimethyl hydroxy Hydroxyethyl ammonium chloride bromide, (C ₁₂ -C ₁₅₎ dimethyl hydroxyethyl ammonium chloride, (C ₁₂ -C ₁₅₎ dimethyl hydroxyethyl ammonium chloride bromide, coconut dimethyl hydroxyethyl ammonium chloride, coconut dimethyl hydroxyethyl ammonium bromide , Myristyl trimethyl ammonium methyl sulfate, lauryl dimethyl benzyl ammonium chloride, lauryl dimethyl benzyl ammonium bromide, lauryl dimethyl (ethenoxy) 4 ammonium chloride, lauryl dimethyl (ethenoxy) 4 ammonium bromide, N-alkyl ( C ₁₂ -C ₁₈ ) dimethylbenzyl ammonium chloride, N-alkyl (C ₁₄ -C ₁₈ ) dimethyl-benzyl ammonium chloride, N-tetradecyldimethylbenzyl ammonium chloride monohydrate, dimethyl didecyl ammonium chloride, N-alkyl (C ₁₂ -C ₁₄₎ dimethyl 1-naphthylmethyl ammonium chloride, trimethylammonium halide al -Trimethylammonium salt, dialkyl-dimethylammonium salt, lauryl trimethyl ammonium chloride, ethoxylated alkylamidoalkyldialkylammonium salt, ethoxylated trialkyl ammonium salt, dialkylbenzene dialkylammonium chloride, N-didecyldimethyl ammonium Chloride, N-tetradecyldimethylbenzyl ammonium chloride monohydrate, N-alkyl (C ₁₂ -C ₁₄ ) dimethyl 1-naphthylmethyl ammonium chloride, dodecyldimethylbenzyl ammonium chloride, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium Chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, C ₁₂ trimethyl ammonium bromide, C ₁₅ trimethylammonium bromide, C ₁₇ trimethyl ammonium bromide, dodecylbenzyl triethyl ammonium chloride, polydiallyldimethylammonium chloride, dimethyl ammonium chloride , Alkyldimeth Tylammonium halogenide, tricetyl methyl ammonium chloride, decyltrimethylammonium bromide, dodecyltriethylammonium bromide, tetradecyltrimethylammonium bromide, methyl trioctylammonium chloride, POLYQUAT 10, tetrabutylammonium bromide, benzyl trimethyl Ammonium bromide, choline esters, benzalkonium chloride, stearalkonium chloride, cetyl pyridinium bromide, cetyl pyridinium chloride, halide salt of quaternized polyoxyethylalkylamine, "MIRAPOL" (polyquater Nium-2), "Alkaquat" (alkyl dimethyl benzylammonium chloride, manufactured by Rhodia), alkyl pyridinium salt, amine, amine salt, imide azolinium salt, protonated quaternary Acrylamide, methylated quaternary polymer, cationic guar gum, benzalkonium chloride, dodecyl trimethyl A monyum bromide, triethanolamine and Paul oxa min may be selected from the group consisting of. However, the present invention is not limited thereto.

The nonionic surfactants herein are SPAN 60, polyoxyethylene fatty alcohol ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene castor oil derivatives, sorbents Non-ester, glyceryl ester, glycerol monostearate, polyethylene glycol, polypropylene glycol, polypropylene glycol ester, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, arylalkyl polyether alcohol, polyoxyethylene polyoxypropylene copolymer , Poloxamer, poloxamine, methylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxy propylcellulose, hydroxy propylmethylcellulose, hydroxypropylmethylcellulose phthalate, amorphous cellulose, polysaccharides, starch, I'm It may be selected from a derivative, hydroxyethyl starch, polyvinyl alcohol, triethanolamine stearate, amine oxides, dextran, glycerol, gum acacia, cholesterol, Bontrager the group consisting of kaenseu, and polyvinylpyrrolidone.

The zwitterionic surfactants herein are N-dodecyl-N, N-dimethyl-3-ammonio-1-propanesulfonate, betaine, alkyl betaine, alkylamido betaine, amido propyl betaine , Coco ampocarboxyglycinate, sacosinate aminopropionate, aminoglycinate, imidazolinium betaine, zwitteridamidolin, N-alkyl-N, N-dimethylammonio-1-propanesulfone Eight, 3-cholamido-1-propyldimethylammonio-1-propanesulfonate, dodecylphosphocholine and sulfo-betaine. However, the present invention is not limited thereto.

According to one embodiment of the present specification, the concentration of the surfactant may be 1 to 5 times or more of the critical micelle concentration (CMC) for the solvent. Specifically, according to one embodiment of the present specification, when water is selected as the solvent, the concentration of the surfactant in the solution may be one or more times five times or less than the critical micelle concentration (CMC) for water. .

According to an exemplary embodiment of the present specification, the concentration of the first surfactant may be at least 1 times and at most 5 times the critical micelle concentration with respect to the solvent. Specifically, the concentration of the first surfactant may be two times the critical micelle concentration with respect to the solvent.

The most important property of a surfactant is that the surfactant has a tendency to adsorb on the interface, such as the air-liquid interface, the air-solid interface and the liquid-solid interface. If the surfactants are free in the sense that they do not exist in agglomerated form, they are called monomers or unimers, and as the unimer concentration is increased they aggregate to form the entity of small agglomerates, ie Form micelles. Such concentration may be referred to as critical micelle concentration.

When the concentration of the surfactant is less than one times the critical micelle concentration, the concentration of the surfactant adsorbed to the first metal salt may be relatively low. Accordingly, the amount of surfactant forming the core to be formed may also be reduced as a whole. On the other hand, when the concentration of the surfactant exceeds 5 times the critical micelle concentration, the concentration of the surfactant is relatively high, and the surfactant forming the hollow core and the metal particles not forming the hollow core may be mixed and aggregated.

According to one embodiment of the present specification, the size of the metal nanoparticles may be controlled by controlling the first and second metal salts surrounding the surfactant and / or micelle forming the micelle.

According to one embodiment of the present specification, the size of the metal nanoparticles may be adjusted by the chain length of the surfactant forming the micelle. Specifically, if the chain length of the surfactant is short, the size of the micelle is small, the hollow size is also small, and thus the size of the metal nanoparticles can be reduced.

According to an exemplary embodiment of the present specification, the carbon number of the chain of the surfactant may be 15 or less. Specifically, the carbon number of the chain may be 8 or more and 15 or less. Alternatively, the carbon number of the chain may be 10 or more and 12 or less.

According to one embodiment of the present specification, the size of the metal nanoparticles may be adjusted by adjusting the type of counter ions of the surfactant forming the micelle. Specifically, the larger the size of the counter ion of the surfactant, the weaker the bonding force with the head portion of the outer end of the surfactant may increase the size of the hollow, thereby increasing the size of the metal nanoparticles.

According to one embodiment of the present specification, when the surfactant is an anionic surfactant, the surfactant may include NH ₄ ⁺ , K ⁺ , Na ⁺ or Li ⁺ as a counter ion.

Specifically, when the counter ion of the surfactant is NH ₄ ⁺ , when the counter ion of the surfactant is K ⁺ , when the counter ion of the surfactant is Na ⁺ , and when the counter ion of the surfactant is Li ⁺ The size of the hollow nanoparticles can be reduced. This can be confirmed by the examples described below.

According to an exemplary embodiment of the present specification, when the surfactant is a cationic surfactant, the surfactant may include I ⁻ , Br ^−, or Cl ⁻ as a counter ion.

Specifically, when the counter ion of the surfactant is I ⁻ , when the counter ion of the surfactant is Br ⁻ , the size of the hollow nanoparticles may be reduced in the order of the counter ion of the surfactant is Cl ⁻ .

According to one embodiment of the present specification, the size of the metal nanoparticles may be adjusted by adjusting the size of the head of the outer end of the surfactant forming the micelle. Furthermore, when the size of the head portion of the surfactant formed on the outer surface of the micelle is increased, the repulsive force between the head portions of the surfactant is increased, so that the hollow can be increased, thereby increasing the size of the metal nanoparticles.

According to an exemplary embodiment of the present specification, the size of the metal nanoparticles can be determined by the combined action of the above-described elements.

According to one embodiment of the present specification, the manufacturing method may be performed at room temperature. Specifically, it may be carried out at a temperature in the range of 4 ° C or more and 35 ° C or less, more specifically 15 ° C or more and 28 ° C or less.

According to one embodiment of the present specification, the forming of the solution may be performed at room temperature, specifically 4 ° C. or more and 35 ° C. or less, more specifically 15 ° C. or more and 28 ° C. or less. If the solvent is an organic solvent, there is a problem that the solvent must be prepared at a high temperature of more than 100 ° C.

According to one embodiment of the present specification, the forming of the solution may be performed for 5 minutes to 120 minutes, more specifically for 10 minutes to 90 minutes, and even more specifically for 20 minutes to 60 minutes.

According to an exemplary embodiment of the present specification, the step of forming the metal nanoparticles by adding a reducing agent to the solution is also performed at room temperature, specifically in the range of 4 ℃ to 35 ℃, more specifically 15 ℃ to 28 ℃ can do.

The forming of the metal nanoparticles is performed by reacting a solution and a reducing agent for a predetermined time, specifically, for 5 minutes to 120 minutes, more specifically for 10 minutes to 90 minutes, and even more specifically for 20 minutes to 60 minutes. can do.

Since the fuel cell catalyst manufacturing method according to the present specification can be manufactured at room temperature, the manufacturing method is simple, and thus, the process is advantageous and the cost reduction effect is large.

According to an exemplary embodiment of the present specification, the reducing agent is a strong reducing agent of the standard reduction -0.23V or less, specifically, -4V or more and -0.23V or less, and reducing power capable of reducing dissolved metal ions to precipitate as metal particles It will not specifically limit, if it has.

Such a reducing agent may be, for example, at least one selected from the group consisting of NaBH ₄ , NH ₂ NH ₂ , LiAlH 4 and LiBEt 3 H.

In the case of using a weak reducing agent, the reaction rate is slow and it is difficult to carry out continuous process such as subsequent heating of the solution, which may cause a problem in mass production. In particular, when a weak reducing agent, ethylene glycol, is used, There is a problem that the productivity in the continuous process is low due to the low flow rate.

According to an exemplary embodiment of the present specification, the forming of the metal nanoparticles may further include adding a nonionic surfactant. In one embodiment of the present invention, the nonionic surfactant is specifically polyoxyethylene fatty alcohol ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene castor oil Derivatives, sorbitan esters, glyceryl esters, glycerol monostearate, polyethylene glycol, polypropylene glycol, polypropylene glycol esters, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, aryl alkyl polyether alcohols, polyoxyethylenepolyoxy Propylene copolymer, poloxamer, poloxamine, methylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxy propylcellulose, hydroxy propylmethylcellulose, hydroxypropylmethylcellulose phthalate, amorphous cellulose , Polysaccharides, starches, starch derivatives, hydroxyethyl starch, polyvinyl alcohol, triethanolamine stearate, amine oxide, dextran, glycerol, acacia gum, cholesterol, tragacanth, and polyvinylpyrrolidone It may be selected.

The nonionic surfactant is adsorbed on the surface of the shell, and serves to uniformly disperse the metal nanoparticles formed in the solution. Therefore, the hollow metal particles are prevented from being aggregated or aggregated and the metal nanoparticles can be formed in a uniform size.

According to one embodiment of the present specification, the forming of the metal nanoparticles may further include a stabilizer.

According to one embodiment of the present specification, the stabilizer may specifically include one or two or more selected from the group consisting of disodium phosphate, dipotassium phosphate, disodium citrate and trisodium citrate.

According to one embodiment of the present specification, the manufacturing method may further include removing a surfactant inside the hollow after forming the metal nanoparticles. The removal method is not particularly limited and may be, for example, a method of washing with water. The surfactant may be an anionic surfactant or a cationic surfactant.

According to one embodiment of the present specification, a method of manufacturing metal nanoparticles may further include removing an first shell including a first metal by adding an acid to the metal nanoparticles after forming the metal nanoparticles. have.

According to one embodiment of the present specification, the acid is not particularly limited, and for example, one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, hydroiodic acid, and hydrobromic acid may be used.

According to one embodiment of the present specification, after the metal nanoparticles are formed, the solution containing the metal nanoparticles may be centrifuged to precipitate the metal nanoparticles included in the solution. Only metal nanoparticles separated after centrifugation can be recovered. If necessary, the firing process of the metal nanoparticles may be additionally performed.

According to one embodiment of the present specification, metal nanoparticles having a uniform size may be manufactured. Conventional methods have made it difficult to produce nanoscale metal nanoparticles, as well as to produce uniform sizes.

One embodiment of the present specification is a cathode; An anode disposed opposite the cathode; And an electrolyte membrane disposed between the cathode and the anode, wherein at least one of the cathode and the anode includes the fuel cell catalyst.

According to one embodiment of the present specification, the cathode may include the catalyst for the fuel cell. Specifically, according to one embodiment of the present specification, the fuel cell catalyst may be a catalyst for a cathode.

In addition, an exemplary embodiment of the present specification provides a fuel cell including the membrane electrode assembly.

According to one embodiment of the present specification, the fuel cell may be a polymer electrolyte fuel cell (PEMFC), a phosphoric acid fuel cell (PAFC), or a direct methanol fuel cell (DMFC).

1 is an exploded perspective view showing an embodiment of a fuel cell. 2 is a schematic cross-sectional view of a membrane electrode assembly (MEA) constituting the fuel cell of FIG. 1.

In the fuel cell 1 shown in FIG. 1, two unit cells 11 are sandwiched by a pair of holders 12 and 12, and the structure is outlined. The unit cell 11 includes a membrane electrode assembly 10 and bipolar plates 20 and 20 disposed on both sides of the membrane electrode assembly 10 in the thickness direction. The bipolar plates 20 and 20 are made of a conductive metal, carbon, or the like, and are bonded to the membrane electrode assembly 10 to function as a current collector and oxygen to the catalyst layer of the membrane electrode assembly 10. And fuel.

In addition, although the number of unit cells 11 is two in the fuel cell 1 shown in FIG. .

As shown in FIG. 2, the membrane electrode assembly 10 includes the electrolyte membrane 100, the catalyst layers 110 and 110 ′ disposed on both sides of the electrolyte membrane 100 in the thickness direction, and the catalyst layers 110 and 110 ′. And gas diffusion layers 120 and 120 'including microporous layers 121 and 121' and supports 122 and 122 ', respectively, stacked on the substrate.

The gas diffusion layers 120 and 120 ′ diffuse oxygen and fuel supplied through the bipolar plates 20 and 20 to the front surface of the catalyst layers 110 and 110 ′, and rapidly discharge water formed in the catalyst layers 110 and 110 ′. It is advantageous to be porous so that the air can be discharged smoothly and the air can flow smoothly. In addition, it is necessary to have conductive conductivity in order to transfer current generated in the catalyst layers 110 and 110 '.

The gas diffusion layers 120 and 120 'are formed of the microporous layers 121 and 121' and the supports 122 and 122 '. The supports 122 and 122 'may be an electrically conductive material, such as a metal or a carbon-based material. For example, a conductive substrate such as carbon paper, carbon cloth, carbon felt or metal cloth may be used, but is not limited thereto.

The microporous layers 121 and 121 'are generally conductive powders having a small particle diameter, such as carbon powder, carbon black, acetylene black, activated carbon, carbon fiber, fullrene, carbon nanotube, carbon nanowire, and carbon. It may include a carbon nanohorn or carbon nano-ring. The conductive powder constituting the microporous layers 121 and 121 ′ may have insufficient pressure diffusion when the particle size is too small, and insufficient diffusion of gas may be difficult when the particle size is too large. Therefore, in consideration of the diffusion effect of the gas, it is possible to use a conductive powder having an average particle diameter in the range of 10 nm to 50 nm in general.

The gas diffusion layers 120 and 120 'may be commercially available products, or may be prepared by purchasing only carbon paper and then directly coating the microporous layers 121 and 121' thereon. The microporous layer 12 is a gas diffusion through the pores formed between the conductive powder, the average pore size of these pores is not particularly limited. For example, the average pore size of the microporous layer 12 may range from 1 nm to 10 μm. For example, the average pore size of the microporous layer 12 may be in the range of 5 nm to 1 μm, in the range of 10 nm to 500 nm, or in the range of 50 nm to 400 nm.

The thickness of the gas diffusion layers 120 and 120 ′ may be in the range of 200 μm to 400 μm in consideration of gas diffusion effects and electrical resistance. For example, the thickness of the gas diffusion layers 120 and 120 ′ may be 100 μm to 350 μm, and more specifically 200 μm to 350 μm.

The catalyst layers 110 and 110 'function as a fuel electrode and an oxygen electrode. The catalyst layers 110 and 110' include the above-described electrode catalyst and a binder for the fuel cell, respectively, and may further include a material capable of increasing the electrochemical surface area of the electrode catalyst. May be included.

The catalyst layers 110 and 110 ′ may have a thickness of 10 μm to 100 μm so as to effectively activate the electrode reaction and not excessively increase the electrical resistance. For example, the catalyst layer 14 may have a thickness of 20 μm to 60 μm, and more specifically, may have a thickness of 30 μm to 50 μm.

The catalyst layers 110 and 110 ′ may further include a binder resin to improve adhesion of the catalyst layer and transfer hydrogen ions. It is preferable to use a polymer resin having hydrogen ion conductivity as the binder resin, and more preferably have a cation exchange group selected from the group consisting of sulfonic acid group, carboxylic acid group, phosphoric acid group, phosphonic acid group and derivatives thereof in the side chain. A polymer resin can be used. Preferably, a fluorine polymer, a benzimidazole polymer, a polyimide polymer, a polyetherimide polymer, a polyphenylene sulfide polymer, a polysulfone polymer, a polyether sulfone polymer, a polyether ketone polymer, a polyether It may include one or more hydrogen ion conductive polymer selected from ether ketone-based polymer, or polyphenylquinoxaline-based polymer.

The catalyst layers 110 and 110 ', the microporous layers 121 and 121' and the supports 122 and 122 'may be disposed adjacent to each other, and layers having different functions may be additionally inserted between the layers as necessary. May be These layers make up the cathode and anode of the membrane electrode assembly.

The electrolyte membrane 100 is disposed adjacent to the catalyst layers 110 and 110 ′. The electrolyte membrane is not particularly limited, for example, polybenzimidazole (PBI), crosslinked polybenzimidazole, poly (2,5-benzimidazole) (ABPBI), polyurethane (Polyurethane) And one or more polymer electrolyte membranes selected from the group consisting of modified polytetrafluoroethylene (modified PTFE).

The electrolyte membrane 100 is impregnated with phosphoric acid or organic phosphoric acid, and other acids other than phosphoric acid may be used. For example, polyphosphoric acid, phosphonic acid (H ₃ PO ₄ ), orthophosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid (H ₄ P ₂ 0 ₇ ), triphosphate (H ₅ P ₃ ) in the electrolyte membrane 100 Phosphate-based materials such as O ₁₀ ), metaphosphoric acid or derivatives thereof may be impregnated. The concentration of these phosphate-based materials is not particularly limited, but may be at least 80% by weight, 90% by weight, 95% by weight, and 98% by weight, for example, an aqueous solution of phosphoric acid of 80 to 100% by weight can be used.

The fuel cell may be composed of a cathode, a cathode, an anode, and a membrane electrode assembly (MEA), and an oxygen reduction reaction (ORR) reaction occurring at the cathode, the cathode, is a rate determining step (RDS) of the entire fuel cell reaction. Can be.

According to an exemplary embodiment of the present specification, the catalyst for the fuel cell is included in the cathode to weaken the strong binding force with the intermediate reactant (OH) generated during the oxygen reduction by the electronic effect of the metal nanoparticles and oxygen storage of ceria ( The role of oxygen storage and the antioxidant effect of Pt can increase the activity of oxygen reduction.

When the catalyst for a fuel cell according to an exemplary embodiment of the present specification is applied as a cathode catalyst, the activity per mass is improved by about 40% compared to a commercially available 20% Pt / C catalyst. In addition, since the ORR at the cathode occurs more easily, the performance of the fuel cell can be improved. Further, the fuel cell catalyst has an advantage of excellent durability. Specifically, it is possible to maintain excellent oxygen reduction activity even after a long time of operation 1000 times or more.

3 illustrates an ORR reaction of a catalyst for a fuel cell according to an exemplary embodiment of the present specification.

In addition to the above effects, the catalyst for a fuel cell according to an exemplary embodiment of the present specification can exert an excellent effect even if the content of expensive platinum is lowered, which is effective in lowering the manufacturing cost of the fuel cell.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present disclosure may be modified in various other forms, and the scope of the present disclosure is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

In order to measure the activity and durability of the catalyst for fuel cells according to one embodiment of the present specification, a half electrode was manufactured to measure the activity and durability of the catalyst for fuel cells. Specifically, a half cell of three electrodes using Ag / AgCl saturated KCl as a reference electrode, Pt wire as a counter electrode, and a glassy carbon rotating electrode having a diameter of 5 mm as a working electrode was prepared. Further, the catalyst ink was prepared using the catalyst for fuel cell, and the catalyst ink was coated on the working electrode to measure the performance of the cathode. The performance of the fuel cell catalyst measured using the half electrode is the same as that in the unit cell. Therefore, the performance of the fuel cell according to the following embodiment is the same as that of the fuel cell catalyst in the unit cell.

Example 1 Preparation of Catalyst for Fuel Cell

0.16 mmol of ammonium carbonate and 120 mg of carbon black were dispersed in 40 mL of water, which was heated to 58 ° C. Here the Ce (NO _{3) 2} was added dropwise a solution of 0.04 mmol was reacted for 24 hours. Thereafter, the mixture was washed twice with water and then heat-treated at 300 ° C. for 4 hours in an air atmosphere to prepare a ceria-doped carbon carrier.

0.1 mmol of Ni (NO ₃ ) ₂ , 0.3 mmol of K ₂ PtCl ₄ , 1.5 mmol of trisodium citrate as stabilizer, 3.2 mmol of lithium dodecylsulfate (LiDS) as surfactant, to 260 ml of water The solution was dissolved to form a solution and stirred for 30 minutes. At this time, the molar ratio of Ni (NO ₃ ) ₂ and K ₂ PtCl ₄ was 3: 1, wherein the concentration of LiDS measured was about twice the critical micelle concentration (CMC) for water. Subsequently, 1.1 mmol of NaBH ₄ , a reducing agent, was added to the solution and allowed to react for 1 hour. The synthesized PtNi metal nanoparticle dispersion was added dropwise to water and a ceria-doped carbon dispersion dispersed in DTAB (Dodecyl Trimethyl Ammonium Bromide), and stirred for 24 hours, followed by adding acetic acid at 70 ° C., stirring for 3 hours, and washing with distilled water. Drying to prepare a catalyst for a fuel cell.

4 and 5 are transmission electron microscope (TEM) images of a catalyst for a fuel cell prepared according to Example 1. FIG.

Example 2 Activity Measurement of Catalysts for Fuel Cells

A catalyst ink was prepared by mixing 2 mg of the fuel cell catalyst prepared in Example 1, 1.6 ml of ethanol, 0.4 ml of distilled water, and 20 µl of a 5 wt% nafion solution. The catalyst ink was dispersed by sonication for 2 hours to prepare a catalyst dispersion.

16 μl of the catalyst dispersion was applied onto a 5 mm diameter glassy carbon rotating electrode (RDE) Rotating Disk Electrode (RDE) and dried at room temperature to form a catalyst layer. In this case, the amount of catalyst formed on the working electrode was 15 µg.

Furthermore, 0.1 M HClO ₄ solution was used as the electrolyte, and cyclic voltage current (Cyclic Voltammetry) was repeated 15 times at a rate of 50 mV / s in the range of 0 to 1.2 V with respect to the standard hydrogen electrode (NHE). After cleaning, the ORR activity experiment was performed. At this time, the potentiostat used was a Versa STAT MC model of Prince Applied Research (PAR).

The ORR activity experiment was conducted at 1,600 rpm and 60 ° C. with oxygen supplied at a rate of 50 cc / min, and 15 times at a rate of 20 mV / s in a range of 0.3 to 1.2 V based on a standard hydrogen electrode (NHE). The last data after the iteration was used.

Comparative Example 1

An ORR activity test was conducted under the same conditions as in Example 2, except that the catalyst for a fuel cell was changed to 20% Pt / C (E-TEK) in Example 2.

ORR measurement results according to Example 2 and Comparative Example 1 are shown in FIG. 6.

In FIG. 6, the x-axis represents the voltage applied by the constant potentiometer, and means that the oxygen reduction reaction occurs more preferably as the voltage moves toward the higher voltage at the same current density value. In Figure 6, when comparing the voltage of Example 2 and Comparative Example 1 at the same current density value, it can be seen that the catalyst for the fuel cell according to Example 2 moved to about 40 mV higher, which is Example 2 The fuel cell catalyst according to the present invention shows better activity than the catalyst for fuel cell of Comparative Example 1.

[Description of the code]

1: fuel cell

10: membrane electrode assembly

11: unit cell

12: holder

100: electrolyte membrane

110, 110 ': catalyst bed

120, 120 ': gas diffusion layer

121, 121 ': microporous layer

122, 122 ': support

Claims (37)

1. A metal nanoparticle comprising a first metal and a second metal comprises a carrier-metal nanoparticle complex supported on a carrier,

   The average particle diameter of the metal nanoparticles is 30 nm or less,

   The carrier is a catalyst for a fuel cell that is doped with ceria (ceria).
2. The method according to claim 1,

   The carrier is a catalyst for a fuel cell is a carbon-based material.
3. The method according to claim 1,

   The ceria is a fuel cell catalyst of 1% by weight or more and 10% by weight or less of the total mass of the carrier.
4. The method according to claim 1,

   The mass ratio of the metal nanoparticles and the carrier is 1: 9 to 4: 6 catalyst for the fuel cell.
5. The method according to claim 1,

   The metal nanoparticles are hollow cores; And a shell part including the first metal and the second metal.
6. The method according to claim 5,

   At least two major peaks representing the atomic percentage of at least one of the first metal and the second metal in the elemental analysis data of the metal nanoparticles.
7. The method according to claim 5,

   When the particle diameter of the metal nanoparticle is 100%,

   At least one major peak indicative of the atomic percentage of the first metal in the region of 0% to 30% from one end point of the particle diameter,

   And at least one other major peak representing the atomic percentage of the first metal in the region of 0% to 30% from the other end point of the particle diameter.
8. The method according to claim 5,

   There are at least two major peaks representing the atomic percentage of the first metal,

   At least two major peaks representing the atomic percentage of the second metal.
9. The method according to claim 5,

   There are at least two major peaks representing the atomic percentage of the first metal,

   A plurality of peaks representing the atomic percentage of the second metal is present in the entire region of the particle size catalyst for a fuel cell.
10. The method according to claim 5,

    The cross-sectional elemental analysis data of the particles is a fuel cell catalyst obtained by using an energy dispersive spectrometer (EDS).
11. The method according to claim 5,

    The volume of the hollow core portion is at least 50% by volume of the total volume of the metal nanoparticles catalyst for fuel cells.
12. The method according to claim 1,

    The metal nanoparticles are hollow cores; A shell part including a first metal and a second metal; And a cavity extending from the outer surface of the shell portion to the hollow core in at least one or more regions of the shell portion.
13. The method according to claim 12,

    The metal nanoparticle is a catalyst for a fuel cell comprising the one cavity.
14. The method according to claim 12,

    The volume of the hollow core portion is at least 50% by volume of the total volume of the metal nanoparticles catalyst for fuel cells.
15. The method according to claim 1,

    The metal nanoparticles of the fuel cell catalyst that comprises one or more tunnels continuous from the outer surface.
16. The method according to claim 15,

    Any one or more of the tunnels penetrate the metal nanoparticles.
17. The method according to claim 15,

    The tunnel is a fuel cell catalyst that is continuous from the outer surface of the metal nanoparticles to an inner region of the metal nanoparticles.
18. The method according to claim 1,

    The metal nanoparticles of the fuel cell catalyst comprising one or more bowl-type particles comprising the first metal and the second metal.
19. The method according to claim 18,

    The metal nanoparticle is a catalyst for a fuel cell comprising one of the bowl-type particles.
20. The method according to claim 18,

    The metal nanoparticle is a catalyst for a fuel cell in which the two bowl-type particles are in contact with each other.
21. The method of claim 20,

    The area in which the bowl-type particles partially contact each other includes a region in which the slope of the tangent is inverted.
22. The method according to claim 1,

    Particle diameter of the metal nanoparticles is a fuel cell catalyst that is within the range of 80% to 120% of the average particle diameter of the metal nanoparticles.
23. The method according to claim 1,

    The metal nanoparticle is a fuel cell catalyst that has a shape containing one or more spherical or bowl-type particles.
24. The method according to claim 1,

    The first metal and the second metal are different from each other, and platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), Palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), A catalyst for a fuel cell selected from the group consisting of titanium (Ti), gold (Au), cerium (Ce), silver (Ag), and copper (Cu).
25. The method according to claim 1,

    One of the first metal and the second metal is platinum (Pt), and the other is nickel (Ni), cobalt (Co), iron (Fe), copper (Cu) or palladium (Pd) Catalyst for fuel cell.
26. Cathode;

    An anode disposed opposite the cathode; And

    An electrolyte membrane disposed between the cathode and the anode,

    At least one of the cathode and the anode is a membrane electrode assembly comprising a fuel cell catalyst according to any one of claims 1 to 25.
27. The method of claim 26,

    The cathode is a membrane electrode assembly comprising the catalyst for the fuel cell.
28. A fuel cell comprising the membrane electrode assembly according to claim 26.
29. Adding a solvent, a first metal salt for providing a first metal ion in the solvent, a second metal salt for providing an atomic group ion containing a second metal ion in the solvent, and at least one surfactant to a solvent to form a solution ; Adding a reducing agent to the solution to form metal nanoparticles; Doping ceria into the carrier; And supporting the metal nanoparticles on the carrier to form a carrier-metal nanoparticle complex,

    The forming of the solution may further include forming the micelle with the surfactant and surrounding the first metal ion and the second metal ion on the outside of the micelle.
30. Doping ceria into the carrier; A solvent is added to form a solution by adding a solvent, a first metal ion in the solvent or a first metal salt providing the first metal ion, a second metal salt providing a second metal ion in the solvent, and at least one surfactant. step; Adding and dispersing ceria-doped carrier to the solution; And adding a reducing agent to the solution to form a carrier-metal nanoparticle complex having metal nanoparticles supported thereon on the carrier doped with ceria,

    The forming of the solution may further include forming the micelle with the surfactant and surrounding the first metal ion and the second metal ion on the outside of the micelle.
31. The method of claim 29,

    The forming of the carrier-metal nanoparticle complex is adding a carrier after the forming of the metal nanoparticles.
32. The method according to claim 29 or 30,

    The surfactant is a method for producing a catalyst for a fuel cell comprising one or two selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants.
33. The method according to claim 29 or 30,

    The first metal salt and the second metal salt are nitrate (Nitrate), halide (Hlide), hydroxide (Hydroxide) or sulfur oxide (Sulfate) of the first metal and the second metal, respectively.
34. The method according to claim 29 or 30,

    The molar ratio of the first metal salt and the second metal salt is 1: 5 to 10: 1 method of producing a catalyst for a fuel cell.
35. The method according to claim 29 or 30,

    The concentration of the surfactant is a method for producing a catalyst for a fuel cell that is at least 1 times 5 times the critical micelle concentration (CMC) for the solvent.
36. The method according to claim 29 or 30,

    The solvent is a method for producing a catalyst for a fuel cell comprising water.
37. The method according to claim 29 or 30,

    The production method is a method for producing a catalyst for a fuel cell that is carried out at room temperature.

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