JP5055788B2 - Electrocatalyst - Google Patents

Electrocatalyst Download PDF

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JP5055788B2
JP5055788B2 JP2006044959A JP2006044959A JP5055788B2 JP 5055788 B2 JP5055788 B2 JP 5055788B2 JP 2006044959 A JP2006044959 A JP 2006044959A JP 2006044959 A JP2006044959 A JP 2006044959A JP 5055788 B2 JP5055788 B2 JP 5055788B2
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catalyst
conductive material
carbon
electrode
particles
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JP2007222732A (en
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継浩 大沼
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日産自動車株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/50Fuel cells
    • Y02E60/52Fuel cells characterised by type or design
    • Y02E60/521Proton Exchange Membrane Fuel Cells [PEMFC]
    • Y02E60/522Direct Alcohol Fuel Cells [DAFC]
    • Y02E60/523Direct Methanol Fuel Cells [DMFC]

Description

  The present invention relates to an electrode catalyst, preferably an electrolyte membrane-electrode assembly (CCM), particularly an electrode catalyst used in an electrolyte membrane-electrode assembly for a fuel cell, a cathode catalyst layer and / or an anode catalyst layer containing the electrocatalyst. The present invention relates to an electrolyte membrane-electrode assembly (CCM) having, in particular, an electrolyte membrane-electrode assembly for a fuel cell, and a fuel cell having the electrolyte membrane-electrode assembly, particularly a solid electrolyte fuel cell. More specifically, the present invention relates to an electrode catalyst that can suppress / prevent corrosion of a conductive material (particularly, a carbon support) in an electrode catalyst in which catalyst particles are supported on a conductive material, preferably an electrolyte membrane-electrode junction. Body (CCM), in particular, an electrode catalyst for use in an electrolyte membrane-electrode assembly for a fuel cell, an electrolyte membrane-electrode assembly (CCM) having a cathode catalyst layer and / or an anode catalyst layer containing the electrocatalyst, particularly a fuel The present invention relates to an electrolyte membrane-electrode assembly for a battery, and a fuel cell having the electrolyte membrane-electrode assembly, particularly a solid oxide fuel cell.

  In recent years, in response to social demands and trends against the background of energy and environmental problems, fuel cells that can operate at room temperature and obtain high output density have attracted attention as power sources for electric vehicles and stationary power sources. A fuel cell is a clean power generation system in which the product of an electrode reaction is water in principle and has almost no adverse effect on the global environment. In particular, the polymer electrolyte fuel cell is expected as a power source for electric vehicles because it operates at a relatively low temperature. In general, the polymer electrolyte fuel cell has a structure in which an electrolyte membrane-electrode assembly is sandwiched between a gas diffusion layer and a separator. The electrolyte membrane-electrode assembly is obtained by sandwiching a polymer electrolyte membrane between a pair of electrode catalyst layers.

In the polymer electrolyte fuel cell having such an electrolyte membrane-electrode assembly, the following electrochemical reaction proceeds. First, hydrogen contained in the fuel gas supplied to the anode side is oxidized by the catalyst component to become protons and electrons (2H 2 → 4H + + 4e ). Next, the generated protons pass through the solid polymer electrolyte contained in the electrode catalyst layer and the polymer electrolyte membrane in contact with the electrode catalyst layer, and reach the cathode side electrode catalyst layer. In addition, the electrons generated in the anode-side electrode catalyst layer are composed of a conductive material constituting the electrode catalyst layer, a gas diffusion layer in contact with a side of the electrode catalyst layer different from the polymer electrolyte membrane, a separator, and an external circuit. To reach the cathode side electrocatalyst layer. The protons and electrons that have reached the cathode-side electrode catalyst layer react with oxygen contained in the oxidant gas supplied to the cathode side to generate water (O 2 + 4H + + 4e → 2H 2 O). In the fuel cell, electricity can be taken out through the above-described electrochemical reaction.

In the electrode catalyst included in the conventional electrode catalyst layer, the cathode side electrode catalyst layer and the anode side electrode catalyst layer are usually refined to a catalyst metal such as platinum or a platinum alloy so as to be high in a carrier having a large specific surface area such as carbon black. A dispersion-supported electrode catalyst is used. Since such an electrode catalyst has a large electrode reaction area on the surface of the catalytic metal, the catalytic activity can be increased. However, the oxygen reduction reaction on the cathode side has a large activation energy, and an overvoltage (resistance) is generated at the cathode, resulting in a noble potential environment of 0.8 V or more, or when the start / stop / continuous operation is repeated. The elution of platinum and the corrosion of the carbon support occur. In particular, on the cathode side, protons obtained from hydrogen on the anode side combine with oxygen supplied to the cathode side to generate water, so that carbon dioxide such as C + 2H 2 O → CO 2 + 4H + + 4e is generated. Is considered to progress. The carbon dioxide generated in this way causes corrosion of the conductive material, and the catalytic metal supported on the surface of the carrier is also liberated and aggregated, resulting in a decrease in catalytic activity and a decrease in battery performance. On the other hand, when fuel shortage occurs on the anode side, water electrolysis or conductive material oxidation occurs in place of the fuel oxidation reaction to maintain the desired current density. However, the conductive material corrodes and disappears, and the catalyst metal is liberated and agglomerated.

For this reason, various studies have been made on means for preventing corrosion of conductive materials and improving life characteristics. For example, carbon black used as a carrier is preheated at a high temperature to increase the degree of crystallinity and increase the graphitization degree with high corrosion resistance. The higher the heat treatment temperature, the better the corrosion resistance. The degree of crystallinity is defined (Patent Documents 1 to 4). In addition, when the heat treatment is performed, the catalyst-supporting carbon is mixed with a substance that promotes graphitization to perform graphitization of the carbon at a low heat treatment temperature, and an activation treatment with water vapor or the like is performed before or after graphitization, There is also a catalyst having a long life and carrying a catalyst noble metal in a highly dispersed state (Patent Document 5).
JP 2000-268828 A JP 2001-357857 A JP 2002-15745 A JP 2003-36859 A JP 2000-273351 A

  As described in Patent Documents 1 to 4, in the method of heat treating carbon black in order to prevent the corrosion of carbon black and improve the life characteristics, the corrosion resistance of carbon black tends to be improved as the heat treatment temperature is higher. . However, at the same time, the BET specific surface area of carbon black tends to decrease, and the platinum fine particles supported on the carbon black have a larger particle size and lower dispersibility as the heat treatment temperature of the carbon black is higher, resulting in lower catalytic activity. As a result, the power generation cell voltage of the fuel cell is lowered. Further, when carbon is graphitized by the method of Patent Document 5, it is necessary to perform activation treatment with water vapor or the like before or after graphitization, and the operation is complicated.

  In any of the above Patent Documents 1 to 5, no investigation has been made on the supported state of the catalyst component supported on the conductive material. The inventor examined the supported state of the catalyst component on the conductive material and found the following. That is, as shown in the upper part of FIG. 1A, there are a part where the catalyst component aggregates and a part where the surface of the carrier is exposed, and the catalyst component is supported unevenly on the carrier as a whole. As shown in the lower part of FIG. 1A, since water easily comes into contact with a portion where the surface of the carrier is exposed, the reaction described above takes place in this portion, and corrosion / deterioration of the conductive material due to carbon dioxide occurs. Occur. Therefore, in a fuel cell having a catalyst layer using such an electrode catalyst, there has been a problem that the catalyst activity and the cell performance are lowered while the start / stop / continuous operation is repeated. In addition, as shown in the upper part of FIG. 1B, there may be a portion where the variation in the catalyst particle diameter is large. In such a case, as shown in the lower part of FIG. 1B, a portion where a large amount of the catalyst component having a small particle diameter is present comes into contact with water, and the reaction described above occurs in such a portion. Since the conductive material is corroded / deteriorated by carbon dioxide, in a fuel cell having a catalyst layer using such an electrode catalyst, the catalytic activity and the cell performance may be degraded while the start / stop / continuous operation is repeated. There was a problem that happened.

  Therefore, the present invention has been made in view of the above circumstances, and can provide an electrode catalyst that can suppress / prevent corrosion / deterioration of a conductive material, thereby having excellent durability and high catalytic activity over a long period of time. With the goal.

  Another object of the present invention is to provide a structure of the electrode catalyst layer (especially, a pore structure) even when there are deterioration factors such as carbon corrosion, elution of catalyst components, deterioration of conductive materials, and tightening pressure of the end plate. It is to provide an electrode catalyst that can maintain the gas diffusibility and the generated water discharge well.

  As a result of intensive studies to solve the above problems, the present inventor has specified that the supported state of the catalyst component supported on the conductive material (particularly the carbon support) is present at a constant interval. The present inventors have found that the corrosion resistance of the carrier can be improved, thereby completing the present invention.

  That is, the above object is that an electrode catalyst in which catalyst particles are supported on a conductive material is adjacent to an arbitrary catalyst particle A, where X is the average particle diameter of the catalyst particles supported on the conductive material. An electrode catalyst characterized in that the catalyst particles are supported on a conductive material such that the center of gravity of each of the three or more catalyst particles is in the range of 0.5X to 2X from the center of gravity of the catalyst particle A. Achieved by:

  According to the present invention, catalyst particles are supported on a conductive material so as to be in a certain dispersed state, thereby suppressing / preventing corrosion of the conductive material that occurs in a high potential state in the presence of the conductive material and water. In addition, the electrode catalyst of the present invention is excellent in durability and exhibits high catalytic activity over a long period of time. Therefore, a fuel cell having a CCM using such an electrode catalyst as a cathode and / or an anode catalyst layer has a catalyst layer during start / stop / continuous operation, particularly a conductive material of the cathode catalyst layer (particularly, a carbon support). Can be effectively prevented / suppressed.

In the first aspect of the present invention, in an electrode catalyst in which catalyst particles are supported on a conductive material, when X is the average particle diameter of the catalyst particles supported on the conductive material, An electrode characterized in that the catalyst particles are supported on a conductive material such that the center of gravity of each of the three or more adjacent catalyst particles is in the range of 0.5X to 2X from the center of gravity of the catalyst particle A. A catalyst is provided. Therefore, in the electrode catalyst of the present invention, as shown in the upper part of FIG. 2, the catalyst particles are present in a highly dispersed state on the conductive material at regular intervals. For this reason, as shown in the lower part of FIG. 2, in the electrode catalyst of the present invention, even when water is generated on the cathode catalyst layer side, the catalyst particles are in contact with water and the conductive material, that is, C + 2H 2 O → CO The reaction of 2 + 4H + + 4e can be effectively suppressed / prevented. At the same time, on the anode side, it is possible to effectively suppress / prevent the fuel oxidation reaction for maintaining a desired current density when the fuel is insufficient. Therefore, the fuel cell using the electrode catalyst of the present invention for the cathode and / or anode catalyst layer, particularly the cathode catalyst layer is excellent in durability and has catalytic activity even after repeated start / stop / continuous operation. Can be suppressed, and therefore excellent battery performance can be maintained over a long period of time. In addition to the advantages described above, the electrode catalyst of the present invention significantly suppresses / prevents the corrosion / deterioration of the conductive material as described above, so that deterioration such as carbon corrosion, elution of catalyst components, and deterioration of the conductive material is caused. The structure of the electrode catalyst layer (especially the pore structure) is not impaired by the factors and end plate clamping pressure, and the structure of the electrode catalyst layer (especially the pore structure) is maintained well. Good discharge of generated water can be maintained.

  Embodiments of the present invention will be described below.

  In the present invention, when the average particle diameter of the catalyst particles supported on the conductive material is X, the center of gravity of each of the three or more catalyst particles adjacent to a certain arbitrary catalyst particle A is the center of gravity of the catalyst particle A. The catalyst particles are supported on the conductive material so that the distance ranges from 0.5X to 2X. In other words, the distance from the center of gravity of any given catalyst particle A is 0.5X to 2X. It is an essential constituent requirement that the catalyst particle group is supported on the conductive material so that the center of gravity of three or more catalyst particles is placed in the range. At this time, if the distance between the center of gravity of each of the three or more adjacent catalyst particles and the center of gravity of the catalyst particle A exceeds 2X, as shown in FIG. Because the exposed area becomes too large, the surface of the conductive material is likely to come into contact with water, especially in this area where the conductive material is significantly corroded / degraded under operating conditions exposed to high potential conditions. It is not preferable. On the other hand, if the distance between the center of gravity of each of the three or more adjacent catalyst particles and the center of gravity of the catalyst particle A is less than 0.5X, the contact between the catalyst particles increases, so the fuel gas / oxidant gas and the electrode catalyst This is not preferable because the three-phase interface between the electrolyte and the electrolyte becomes small and the catalytic activity is lowered. In the present invention, the distance (Y) between the center of gravity of each of the three or more adjacent catalyst particles and the center of gravity of the catalyst particle A is expressed by the following formula with respect to the average particle diameter of the catalyst particles carried on the conductive material as X. Is preferably satisfied.

  In this specification, “the distance between the center of gravity of each of the three or more adjacent catalyst particles and the center of gravity of the catalyst particle A” is an index indicating the dispersion state of each catalyst particle supported on the conductive material. is there. Therefore, when the particle diameters of the catalyst particles are the same, for example, as shown in FIG. 3B, the catalyst particles A (the middle circle in FIG. 3B) and the four catalyst particles adjacent to each other When each circumference is in contact with the circumference of the catalyst particle A, the distance (Y) between the center of gravity of the adjacent catalyst particles and the center of gravity of the catalyst particles A is 1.0X. When the center of gravity of the four catalyst particles adjacent to the catalyst particle A exists on the circumference of the catalyst particle A as shown in FIG. 3A, the distance (Y) is described as 0.5X. The Furthermore, as shown in FIG. 3D, when the distance between the center of gravity of the catalyst particle A and the center of gravity of the catalyst particle A is twice the particle size of the catalyst particle A, the distance (Y) is 2. It is described as 0X. In FIG. 3, since the catalyst particles are assumed to be spherical, the center of gravity and the center are the same. As is clear from FIG. 3, the catalyst particle occupancy (unit) when the distance (Y) between the center of gravity of the adjacent catalyst particles and the center of gravity of the catalyst particles A is in the range of 0.5X to 2X. The ratio (%) of the area occupied by the catalyst particles per lattice is 14.9 to 81.0%.

  In this case, the “average particle diameter of the catalyst particles” is a crystallite diameter obtained from the half width of the diffraction peak of the catalyst component in X-ray diffraction or a particle diameter of 100 to 1000 catalyst particles examined from a transmission electron microscope image. The average value can be measured. However, in this specification, “the average particle diameter X of the catalyst particles” is an average value of the particle diameters of 100 catalyst particles examined from a transmission electron microscope (TEM) image.

  In the present invention, when the average particle diameter of the catalyst particles carried on the conductive material is X and the catalyst particles are assumed to be spherical with a diameter X, the area S1 where the catalyst particles per 1 g occupy the conductive material. Surface area S2 of the conductive material per gram (where S2 excludes the surface area in the pores having a pore diameter X or less), the mass fraction G1 of the catalyst component in the electrode catalyst, and the conductivity in the electrode catalyst The mass fraction G2 of the material preferably satisfies the formula: (S1 · G1) / (S2 · G2) = 0.2 to 1.35. When the catalyst particles cover the conductive material at such a ratio, the electrode catalyst can simultaneously achieve a sufficient effect of inhibiting / preventing corrosion of the conductive material and a sufficient catalytic activity. On the other hand, if the value of the formula: (S1 · G1) / (S2 · G2) is less than 0.2, the area of the catalyst particles occupying the surface of the conductive material is small. In some cases, the conductive material is likely to corrode and deteriorate. On the other hand, if (S1 · G1) / (S2 · G2) exceeds 1.35, the surface of the conductive material is filled or laminated with the catalyst material, which may reduce the utilization rate of the catalyst particles. The value of the formula: (S1 · G1) / (S2 · G2) is preferably 0.2 to 1.0, most preferably 0.2 to 0.8.

In the present specification, “value of formula: (S1 · G1) / (S2 · G2)” is an index indicating the ratio of the conductive material covered with the catalyst particles, and the fact that this value is small means that the conductivity is low. This means that the area of the catalyst particles on the surface of the material is small, that is, the exposed area of the surface of the conductive material is large. In the above formula, S1 is an area in which the catalyst particles per 1 g occupy the conductive material. For example, when 1 g of catalyst particles having an average particle diameter a (nm) is b (pieces), S1 = (a 2 π / 4) × b. Here, when platinum particles were used as the catalyst particles, the average particle diameter X (nm) and the area occupied by the conductive material per 1 g of platinum particles (S1: m 2 / g) were measured and shown in FIG. The result was obtained. From this, it can be seen that S1 decreases as the average particle diameter (X) of the platinum particles increases. FIG. 4 is a plot of S1 (m 2 / g) (vertical axis) against average particle diameter X (nm) (horizontal axis). S2 is the BET area of the conductive material. For example, when 30% by mass of platinum particles are supported on a conductive material, G1 = 0.3 and G2 = 0.7.

  The shape and size of the catalyst particles are not particularly limited, and the same shape and size as known catalyst particles can be used. For example, the catalyst particles include substantially granular shapes and elliptical shapes. At this time, the smaller the average particle diameter X of the catalyst particles, the higher the effective electrode area where the electrochemical reaction proceeds, and the higher the oxygen reduction activity. However, in practice, if the average particle diameter is too small, the oxygen reduction activity There is a phenomenon that decreases. Therefore, the average particle diameter X of the catalyst particles is preferably 1 to 10 nm, more preferably 2 to 8 nm, and most preferably 3 to 5 nm. From the viewpoint of easy loading and elution of the catalyst component, it is preferably 1 nm or more. The specific surface area of the catalyst (that is, catalytic activity) and the dispersion state of the catalyst particles as described above on the conductive material (that is, From the viewpoint of (suppression of corrosion / deterioration of conductive material), it is preferably 10 nm or less. In particular, when the average particle diameter of the catalyst particles is large, the interval between the catalyst particles becomes large. Therefore, when a conductive material, for example, a carbon material is used, contact between the carbon support surface and water easily occurs, and the operating conditions Below, it is not preferable because significant carbon corrosion may occur.

  In the present invention, it is preferable that the variation (distribution) of the particle diameter of the catalyst particles supported on the conductive material is in the range of 0.75X to 1.5X. When the variation in the particle diameter of the catalyst particles is within such a range, the catalyst particles are effectively eluted and recrystallized, and further, the contact between the conductive material and water is effectively achieved by the catalyst particles appropriately supported on the conductive material. Since it can be suppressed / prevented, deterioration of the conductive material can be effectively suppressed / prevented. On the other hand, when the variation of the catalyst particles is not within the above range, the small particles are eluted under the operating conditions in which the catalyst particles are eluted, and re-deposited in the electrolyte membrane or on the surface of the large particles. May end up. Further, when re-deposited on the surface of such a large particle, the specific surface area of the catalyst is reduced, which may cause a reduction in the specific activity of the catalyst. Further, when the eluted particles are deposited in the film, it may cause a deterioration of the film, which is not preferable. Furthermore, when the variation of the catalyst particles is not within this range, there is a high possibility that the interval between the catalyst particles becomes large, and the conductive material and water may easily come into contact with each other.

  In the present invention, when the catalyst particles constituting the catalyst layer are used in the cathode catalyst layer, any known catalyst can be used in the same manner as long as it has a catalytic action in the oxygen reduction reaction. Also, the catalyst particles used in the anode catalyst layer are not particularly limited as long as they have a catalytic action in the oxidation reaction of hydrogen, and known catalysts can be used in the same manner. Specifically, selected from platinum, ruthenium, iridium, rhodium, palladium, osmium, tungsten, lead, iron, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, aluminum, and alloys thereof, and the like Preferably, metals such as platinum, palladium, rhodium, ruthenium, iridium, cobalt, nickel, iron, chromium and manganese, and alloys thereof are preferably used. Among these, those containing at least platinum are preferably used in order to improve catalyst activity, poisoning resistance to carbon monoxide and the like, heat resistance, and the like. The composition of the alloy is preferably 30 to 90 atomic% for platinum and 10 to 70 atomic% for the metal to be alloyed, depending on the type of metal to be alloyed. The composition of the alloy when the alloy is used as a cathode catalyst varies depending on the type of metal to be alloyed and can be appropriately selected by those skilled in the art, but platinum is 30 to 90 atomic%, and other metals to be alloyed are 10 It is preferable to set it to -70 atomic%. In general, an alloy is a generic term for a metal element having one or more metal elements or non-metal elements added and having metallic properties. The alloy structure consists of a eutectic alloy, which is a mixture of the component elements as separate crystals, a component element completely melted into a solid solution, and a component element composed of an intermetallic compound or a compound of a metal and a nonmetal. There is what is formed, and any may be used in the present application. At this time, the catalyst particles used for the cathode catalyst layer and the catalyst particles used for the anode catalyst layer can be appropriately selected from the above. In the following description, unless otherwise specified, the descriptions of the catalyst particles for the cathode catalyst layer and the anode catalyst layer have the same definition for both, and are collectively referred to as “catalyst particles”. However, the catalyst particles for the cathode catalyst layer and the anode catalyst layer do not need to be the same, and are appropriately selected so as to exhibit the desired action as described above.

  In the present invention, the conductive material may be any material as long as it has a specific surface area for supporting the catalyst particles in a desired dispersed state and sufficient electronic conductivity as a current collector. Is preferably carbon. Specific examples include carbon particles such as carbon black such as acetylene black, ketjen black, and talker black, graphite such as activated carbon, coke, natural graphite, and artificial graphite, carbon nanofiber, and carbon nanotube. Among these, acetylene black, ketjen black, talker black, activated carbon, graphite, carbon nanofiber, and carbon nanotube are preferable as the conductive material. Under the present circumstances, the said electroconductive material may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture. In the present invention, “the main component is carbon” refers to containing a carbon atom as a main component, and is a concept including both a carbon atom only and a substantially carbon atom. In some cases, elements other than carbon atoms may be included in order to improve the characteristics of the fuel cell. In addition, being substantially composed of carbon atoms means that mixing of impurities of about 2 to 3% by mass or less is allowed.

The BET specific surface area of the conductive material may be a specific surface area sufficient to carry the catalyst particles in a highly dispersed manner, but is preferably 30 to 500 m 2 / g, more preferably 100 to 300 m 2 / g. Is good. If the specific surface area is in such a range, good dispersibility of the catalyst particles and the polymer electrolyte in the conductive material can be maintained, the effective utilization rate of the catalyst particles and the polymer electrolyte can be improved, and sufficient power generation performance can be achieved. Can be achieved.

  In addition, the size of the conductive material is not particularly limited, but from the viewpoint of controlling the ease of loading, the catalyst utilization, and the thickness of the electrode catalyst layer within an appropriate range, the average particle size is 5 to 200 nm. The thickness is preferably about 10 to 100 nm.

  Alternatively, the conductive material grows protrusions mainly composed of carbon from the surface of multi-branched carbon nanofibers or carbon nanotubes (CNT) in which protrusions mainly composed of carbon are grown from the surface of carbon nanofibers (CNF). It is preferable that the multi-branched carbon nanotubes include at least one of the multi-branched carbon nanotubes, or at least one of the multi-branched carbon nanofibers or the multi-branched carbon nanotubes. Under the present circumstances, the said electroconductive material may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture. Conventionally, the electrode catalyst layer undergoes various changes such as corrosion of conductive materials (especially carbon), catalyst elution, and electrolyte degradation due to load operation. It has been a factor that significantly reduces the power generation function, affecting the diffusion of water and the discharge of produced water. However, when multi-branched carbon nanofibers and / or multi-branched carbon nanotubes are used as the conductive material in this way, as shown in FIG. 5, the multi-branched carbon nanofibers / multi-branched carbon nanotubes with protrusions grown thereon are electrically conductive. When used as a conductive material, the catalyst particles are more firmly supported on the branched parts of multi-branched carbon nanofibers / multi-branched carbon nanotubes than when two-dimensional CNF / CNT that does not grow protrusions is used. At the same time, as described in detail below, when an electrode catalyst is used in the catalyst layer, the entanglement with the ion conductive material (electrolyte) is good, so that deformation of the catalyst layer can be significantly suppressed / prevented. . In addition, multi-branched carbon nanofibers / multi-branched carbon nanotubes are advantageous in terms of gas diffusibility and drainage because (i) the specific surface area is larger than conventional CNF / CNT; Unlike carbon fiber, etc., which do not grow any protrusions, the protrusions grow at an angle close to the perpendicular to the fiber growth direction, so that the catalyst particles can be supported firmly and easily, and the surface is solid and dense. Since the catalyst particles can be supported by the conductive material itself, the carbon corrosion resistance of the conductive material itself can be increased. (Iii) Compared to the conventional CNF / CNT, the specific surface area is high and the catalyst particles can be easily supported. / An electrode catalyst layer including an electrode catalyst in which catalyst particles are supported on multi-branched carbon nanotubes has an advantage that excellent performance can be exhibited. Furthermore, unlike multi-branched carbon nanofibers / multi-branched carbon nanotubes, etc., where normal protrusions do not grow, protrusions (three-dimensional) grow at an angle close to perpendicular to the fiber growth direction. Therefore, it is possible to suppress biting into the membrane when transferring the electrode catalyst layer to the electrolyte membrane. For this reason, an electrode catalyst layer including an electrocatalyst using such multi-branched carbon nanofibers / multi-branched carbon nanotubes as a conductive material can maintain its structure better, and the deterioration and tightening pressure of the catalyst layer Even when the catalyst layer is deformed, it is possible to effectively prevent the electrolyte membrane from being damaged.

  In the present invention, the method for producing multi-branched carbon nanofibers / multi-branched carbon nanotubes when using multi-branched carbon nanofibers / multi-branched carbon nanotubes as the conductive material is not particularly limited, and is a normal carbon growth method. Can be used. For example, after a catalyst supporting the vapor phase growth of carbon, such as fine Ni or Fe, is supported on the surface of carbon nanofiber / carbon nanotube, the gas of carbon is vaporized by chemical vapor deposition (CVD) based on the catalyst. By performing phase growth, branch-like carbon grows from the surface of the carbon nanofiber / carbon nanotube. Alternatively, the multi-branched carbon nanofiber / multi-branched carbon nanotube may be a commercially available product.

  In the present invention, when multi-branched carbon nanofibers / multi-branched carbon nanotubes are used for the conductive material, the size of the multi-branched carbon nanofibers / multi-branched carbon nanotubes is not limited as long as the catalyst particles can be supported favorably. Although not particularly limited, for example, a material having a diameter of 10 to 200 nm, more preferably 10 to 100 nm, and a length of 20 nm to 2 μm, more preferably 20 to 500 nm is preferably used. Further, the interval between the branches of the multi-branched carbon nanofiber / multi-branched carbon nanotube can be appropriately selected as long as the catalyst particles can be favorably supported and do not interfere with the catalytic activity.

  In the electrode catalyst in which catalyst particles are supported on the conductive material, the supported amount of the catalyst particles is preferably 5 to 80% by mass, more preferably 10 to 50% by mass with respect to the total amount of the electrode catalyst. Good. When the supported amount is in the above range, the catalyst particles can be favorably dispersed on the conductive material, and improvement in power generation performance can be expected. The amount of catalyst particles supported can be examined by inductively coupled plasma emission spectroscopy (ICP).

  Further, the catalyst particles can be supported on the conductive material by a known method. For example, known methods such as impregnation method, solution reduction (liquid phase reduction support) method, evaporation to dryness method, colloid adsorption method, spray pyrolysis method, reverse micelle (microemulsion method) can be used, but preferably solution reduction The method is used. Hereinafter, although the method of manufacturing the electrode catalyst of this invention using a solution reduction method is explained in full detail, the electrode catalyst of this invention is not limited to what is manufactured by the following manufacturing method.

  As a solution reduction method preferably used in the present invention, a reducing agent and a precursor solution of catalyst particles are added to the conductive material, and the mixture is stirred and mixed at 25 to 50 ° C. for a predetermined time, preferably 30 to 120 minutes. Thereafter, using an ultrasonic homogenizer or the like, further dispersed and mixed for a predetermined time, preferably 10 to 30 minutes, at 25 to 50 ° C. to obtain a uniform dispersion, and then the dispersion is processed for a predetermined time, preferably Reduction treatment is performed at 60 to 95 ° C. for 1 to 12 hours to support the catalyst particles on the conductive material.

In the above method, as the reducing agent, ethanol, methanol, propanol, formic acid, formate such as sodium formate and potassium formate, formaldehyde, sodium thiosulfate, citric acid, sodium borohydride (NaBH 4 ) and hydrazine (N 2 H 4 ) and the like can be used, and ethanol, methanol, propanol, formic acid, formaldehyde, sodium thiosulfate, citric acid, sodium borohydride and hydrazine can be preferably used. At this time, the amount of the reducing agent added is not particularly limited as long as it is an amount capable of sufficiently reducing the catalyst particle precursor described in detail below and supporting it on the conductive material. In contrast, it is preferable to add 1 to 200 moles of the reducing agent.

  Further, the precursor of the catalyst particles can be appropriately selected depending on the type of metal used for the catalyst particles. For example, when noble metal particles are used as catalyst particles, examples of the noble metal ion source include nitrates such as rhodium nitrate and palladium nitrate, nitrates such as chloroplatinic acid and dinitrodiammine platinum, sulfates, ammonium salts, amines, Ammine salts such as tetraammineplatinum and hexaammineplatinum, carbonates, bicarbonates, bromides such as platinum chloride and palladium chloride, halides such as chloride, inorganic salts such as nitrite and oxalic acid, carboxylates such as formate And compounds capable of forming noble metal ions in an aqueous solution, such as hydroxides, alkoxides and oxides, are preferred. Of these, noble metals such as chloroplatinic acid and nitrate of dinitrodiammine platinum are preferably used. When transition metal particles are used as catalyst particles, for example, halides such as nitrates, dinitrodiammine salts, sulfates, ammonium salts, amines, carbonates, bicarbonates, bromides, chlorides of the above transition metals. Inorganic salts such as nitrite and succinic acid, carboxylates such as formate and hydroxides, alkoxides, oxides, and the like are preferable compounds that can become transition metal ions in an aqueous solution. Of these, transition metal halides, particularly chlorides, nitrates, and dinitrodiammine salts are preferably used, and nitrates are particularly preferred. The catalyst particle precursor may be a single precursor or a mixture of two or more.

  In the above method, the amount of the conductive material is not particularly limited as long as a desired amount of catalyst particles is supported.

  The dispersion thus obtained is subjected to a reduction treatment for a predetermined time. In the step of supporting the catalyst particles on the conductive material using the solution reduction method, the catalyst component is reduced with a reducing agent. At this time, it is preferable to introduce carbon monoxide gas. When carbon monoxide gas is introduced into the above mixed solution by bubbling or the like, the catalyst particle precursor is reduced with a reducing agent and supported on the conductive material. Since carbon monoxide adheres to the surface of the particle precursor (particularly platinum) and prevents aggregation of the particles, the catalyst particles can be supported on the conductive material in the desired dispersion state as described above. At this time, the carbon monoxide gas may be composed of carbon monoxide alone or mixed with a gas such as nitrogen, helium, air, etc., but preferably in a concentration of 10 to 100% by volume in nitrogen. More preferably, a mixed gas containing carbon monoxide at a concentration of 50 to 100% by volume in air is used. Further, the inflow rate of the carbon monoxide gas is not particularly limited as long as the above effects can be achieved.

  Finally, after the reduction reaction is completed, the solution is filtered to separate the solid content, linearized with pure water or the like, and dried, whereby the catalyst particles are dispersed on the conductive material according to the present invention. The electrode catalyst supported by the above is obtained.

  In the present invention, in addition to the above catalyst particles, a catalyst having water electrolysis activity is preferably coexistingly supported on the conductive material. At this time, the catalyst having water electrolysis activity is composed of components different from the catalyst particles. Further, the catalyst having water electrolysis activity does not need to satisfy the dispersion state of the catalyst particles, which is an essential constituent element of the present invention, and any dispersion is possible as long as the effects described in detail below are exhibited. It may be in a state. According to the present invention, by supporting the catalyst particles under certain conditions, it is possible to suppress carbon corrosion that occurs in a high potential state in the presence of a conductive material and water. However, even in this state, it is not possible to completely prevent water from entering the voids between the catalyst particles, or the reaction occurs when water vapor or oxidant gas (especially oxygen) contained in the fuel gas or oxidant gas enters. In some cases, it is not possible to completely prevent / suppress the presence of generated water. For this reason, a small amount of water exists between the catalyst particles, and the corrosion of the conductive material may occur to some extent. In such a case, as described above, in addition to the catalyst particles, such a small amount of water can be efficiently decomposed by supporting a catalyst having water electrolysis activity on the conductive material. Thus, corrosion of the conductive material can be more effectively suppressed / prevented. As described above, the present invention is mainly characterized in that the catalyst particles are present in a certain distance range on the conductive support. Even in such a case, the catalyst particles are shown in FIG. Thus, as a matter of course, when the catalyst particles are supported on the conductive material at a substantially constant predetermined distance (the upper left in FIG. 6), the catalyst particles vary within a predetermined distance range according to the present invention. There is a case where it is supported on the conductive material while maintaining the above-mentioned distance (with a somewhat uneven dispersion state) (upper right in FIG. 6). Even in such a case, if the catalyst having water electrolysis activity is supported on the conductive material, the catalyst having water electrolysis activity can be present between the catalyst particles at some distance (see FIG. (Refer to the bottom row of 6). For this reason, even if small water molecules enter between the catalyst particles, the presence of water can be more effectively suppressed / prevented by the presence of the catalyst having water electrolysis activity.

  The catalyst having water electrolysis activity that can be used in the present invention is not particularly limited as long as it has water electrolysis activity. Examples thereof include iridium oxide, ruthenium oxide, iridium, ruthenium, and an alloy of iridium and ruthenium. Of these, iridium oxide, ruthenium oxide, iridium or ruthenium is preferred. In particular, from the viewpoint of catalyst activity and carbon corrosion resistance, platinum catalyst particles that are catalyst particles and iridium oxide that has high water electrolysis activity and excellent elution resistance should be supported on a conductive material as a catalyst having water electrolysis activity. Is preferred.

  The shape and size of the catalyst having water electrolysis activity are not particularly limited, and the same shape and size as known catalysts can be used. For example, the catalyst having water electrolysis activity includes substantially granular and elliptical shapes. At this time, the average particle diameter of the catalyst having water electrolysis activity in the case of a granular form is not particularly limited, but is preferably smaller than the average particle diameter of the catalyst particles so as to enter between the catalyst particles. Therefore, the catalyst having water electrolysis activity is preferably in the form of particles having an average particle diameter of 0.3 to 20 nm, more preferably 0.5 to 2 nm. If it is such a range, the catalyst which has water electrolysis activity will penetrate | invade between catalyst particles easily, and can electrolyze the water which exists on an electroconductive material depending on the case efficiently.

  In the present invention, when the catalyst having water electrolysis activity co-supports on the catalyst particles and the conductive material, the presence ratio of the catalyst having water electrolysis activity is a ratio that exhibits the above-described effects. There is no particular limitation. Specifically, the catalyst having water electrolysis activity is 5 to 50% by mass, more preferably 5 to 33% by mass, and most preferably 10 to 20% by mass with respect to the catalyst particles present on the same conductive material. %. The amount of the catalyst having water electrolysis activity is, for example, when platinum as catalyst particles and iridium as a catalyst having water electrolysis activity are present at a mass ratio of 2: 1 (Pt: Ir = 2: 1). Is 50% by mass. When a catalyst having water electrolysis activity is present in such an amount, the water entering between the catalyst particles is decomposed while maintaining sufficient catalyst activity, and the corrosion of the conductive material is effectively suppressed simultaneously. Can be prevented.

Further, when the catalyst having water electrolysis activity is co-supported on the catalyst particles and the conductive material, the catalyst having water electrolysis activity is on the conductive material either before or after the catalyst particle supporting step as described above. However, it is preferably after the catalyst particle supporting step. This is because a catalyst having water electrolysis activity can be efficiently present in the gaps between the catalyst particles after the catalyst particles are supported. At this time, the method for supporting the catalyst having water electrolysis activity on the conductive material is not particularly limited, and a known supporting method can be used in the same manner or after modification. For example, when iridium or ruthenium is used as a catalyst having water electrolysis activity, the above-described method for supporting catalyst particles can be used in the same manner. When iridium oxide or ruthenium oxide is used as a catalyst having water electrolysis activity, a solution reduction method, a heating oxidation method, an electrodeposition method, or the like can be preferably used in addition to the above method. At this time, in the solution reduction method, for example, an aqueous solution of iridium nitrate or iridium chloride is used as an iridium precursor, and a reducing agent such as ethanol, methanol, propanol, formic acid, formaldehyde, ascorbic acid, sodium thiosulfate, A reducing agent such as citric acid is mixed, heated and stirred at about 90 ° C. for 4 hours, filtered, and dried to support the iridium precursor or iridium. Furthermore, it can carry | support as iridium oxide by heat-processing between 150 degreeC-400 degreeC in oxygen-containing atmosphere. Further, the heating oxidation method is not particularly limited. For example, iridium chloride (IrCl 4 · H 2 O), iridium chloride (H 2 IrCl 6 · 6H 2 O), and iridium resin acid are mixed with water, ethanol, An iridium precursor solution is prepared by dissolving in a solvent such as butanol. The iridium precursor solution is applied to a conductive material supported by catalyst particles within a predetermined distance range, and this is applied to an oxygen atmosphere (for example, oxygen content). A method of heat-treating at a temperature of 200 to 800 ° C. for 5 to 10 minutes under a condition of a pressure of 0.1 to 0.5 atm) is preferably used. The electrodeposition method is not particularly limited. For example, an iridium oxide (for example, an iridium oxide (for example, by immersing a conductive material supported by catalyst particles in a predetermined distance range in an aqueous solution of Na 2 IrO 4 ) The method of electrodepositing IrO 2 ) can be used, and in the above method, a method of supporting iridium oxide on a conductive material as a catalyst having water electrolysis activity has been described in detail, but other water electrolysis such as ruthenium oxide is used. The same method can be used for the active catalyst.

  The electrode catalyst thus obtained can suppress / prevent corrosion of the conductive material that occurs in a high potential state in the presence of water, has excellent durability, and exhibits high catalytic activity over a long period of time. Therefore, the CCM obtained by using the electrode catalyst of the present invention for the cathode and / or anode catalyst layer is used for the catalyst layer during start / stop / continuous operation, particularly the conductive material of the cathode catalyst layer (particularly the carbon support). ) Can be effectively prevented / suppressed, so that it is useful for applications where such an effect is desired, particularly for an electrolyte membrane-electrode assembly (CCM) for a fuel cell. That is, the second of the present invention is an electrolyte membrane having an electrolyte membrane, a cathode catalyst layer disposed on one side of the electrolyte membrane, and an anode catalyst layer disposed on the other side of the electrolyte membrane. An electrode assembly comprising an electrolyte membrane-electrode assembly, wherein the electrode catalyst of the present invention is used in at least one of a cathode catalyst layer and an anode catalyst layer. The third aspect of the present invention is to provide a fuel cell using such an electrolyte membrane-electrode assembly.

  An electrolyte membrane-electrode assembly (CCM) of the present invention comprises an electrolyte membrane, a cathode catalyst layer disposed on one side of the electrolyte membrane, and an anode catalyst layer disposed on the other side of the electrolyte membrane. And the electrode catalyst of the present invention is used for at least one of the cathode and anode catalyst layers. At this time, as described above, in order to generate water on the cathode side, the electrode catalyst of the present invention is preferably used in at least the cathode catalyst layer.

  In addition, when not using the electrode catalyst of this invention for a catalyst layer, the catalyst similar to an electrode catalyst known in the said field | area can be used, and each gravity center of three or more adjacent catalyst particles and the gravity center of the catalyst particle A can be used. It is the same as the electrode catalyst of the present invention, except that there is no limitation on the distance to

  In the present invention, the cathode catalyst layer / anode catalyst layer (hereinafter also simply referred to as “catalyst layer”) contains an ion conductive substance in addition to the electrode catalyst (the catalyst particles are supported on the conductive material). . The ion conductive material is not particularly limited, and a known material can be used, but any member having at least high proton conductivity may be used. Ion conductive materials that can be used in this case are broadly classified into fluorine-based electrolytes containing fluorine atoms in all or part of the polymer skeleton and hydrocarbon-based electrolytes not containing fluorine atoms in the polymer skeleton.

  Specific examples of the fluorine electrolyte include perfluorocarbon sulfonic acids such as Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Co., Ltd.), and Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.). Polymer, Gore Select (registered trademark, manufactured by Japan Gore-Tex Co., Ltd.), polytrifluorostyrene sulfonic acid polymer, perfluorocarbon phosphonic acid polymer, trifluorostyrene sulfonic acid polymer, ethylenetetrafluoroethylene-g-styrene sulfonic acid Preferable examples include a polymer, an ethylene-tetrafluoroethylene copolymer, and a polyvinylidene fluoride-perfluorocarbon sulfonic acid polymer.

  Specific examples of the hydrocarbon electrolyte include polysulfone sulfonic acid, polyaryl ether ketone sulfonic acid, polybenzimidazole alkyl sulfonic acid, polybenzimidazole alkyl phosphonic acid, polystyrene sulfonic acid, polyether ether ketone sulfonic acid, polyphenyl. A suitable example is sulfonic acid.

  The ion conductive substance preferably contains a fluorine atom because of its excellent heat resistance and chemical stability. Among them, Nafion (Nafion registered trademark, manufactured by DuPont), Aciplex (registered trademark, Asahi Kasei Corporation) And fluorine electrolytes such as Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.).

  The electrolyte membrane used in the CCM of the present invention is not particularly limited, and examples thereof include a polymer electrolyte membrane made of the same conductive material as that used for the catalyst layer. In addition, perfluorosulfonic acid membranes represented by various Nafion (registered trademark) and Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.) manufactured by DuPont, ion exchange resins (Dawex, registered trademark) manufactured by Dow Chemical Company, Fluorine polymer electrolytes such as ethylene-tetrafluoroethylene copolymer resin membranes, resin membranes based on trifluorostyrene, and hydrocarbon resin membranes having sulfonic acid groups are generally commercially available. A solid polymer electrolyte membrane, a membrane in which a polymer microporous membrane is impregnated with a liquid electrolyte, a membrane in which a porous body is filled with a polymer electrolyte, and the like may be used. The polymer electrolyte used for the electrolyte membrane and the polymer electrolyte used for each catalyst layer may be the same or different from the viewpoint of improving the adhesion between each catalyst layer and the electrolyte membrane. It is preferable to use the same one.

  The thickness of the electrolyte membrane may be appropriately determined in consideration of the characteristics of the obtained CCM, but is preferably 5 to 300 μm, more preferably 10 to 200 μm, and particularly preferably 15 to 100 μm. From the viewpoint of strength during film formation and durability during CCM operation, it is preferably 5 μm or more, and from the viewpoint of output characteristics during CCM operation, it is preferably 300 μm or less.

  Further, as the electrolyte membrane, in addition to the above-described fluorine-based polymer electrolyte and a membrane made of a hydrocarbon resin having a sulfonic acid group, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc. You may use what formed the porous thin film impregnated with electrolyte components, such as phosphoric acid and an ionic liquid.

  The method for producing the CCM of the present invention is not particularly limited, and a method similar to a conventionally known method can be applied except that the electrode catalyst of the present invention is added to the cathode catalyst layer and / or the anode catalyst layer as described above. . For example, a catalyst ink prepared from the electrode catalyst of the present invention and an ion conductive material is applied and dried at a desired thickness on a transfer mount, thereby forming a catalyst layer on the cathode side and the anode side, respectively. The electrolyte membrane is sandwiched between the catalyst layers so that the catalyst layer is on the inside and bonded by hot pressing or the like, and then the transfer mount is peeled off to obtain a CCM.

  Hereinafter, preferred embodiments of the method for producing CCM of the present invention will be described. In addition, the following aspect shows the preferable aspect of this invention, The manufacturing method of CCM of this invention is not limited to the following method, The electrode catalyst of this invention is used for both a cathode and an anode catalyst layer. The production method for use will be described. As described above, it is not necessary to use the electrode catalyst of the present invention for both the cathode and anode catalyst layers. In such a case, a known electrode catalyst may be used. .

  First, an electrode catalyst, an ion conductive material, and a solvent are mixed together to prepare a cathode / anode catalyst ink. Here, it is preferable to further add a reinforcing material to at least one of the cathode catalyst layer and the anode catalyst layer. By adding a reinforcing material, the structure of the catalyst layer can be maintained better as described in the section of the conductive material, and even when the catalyst layer is deformed due to deterioration or clamping pressure of the catalyst layer. It is possible to effectively prevent the electrolyte membrane from being damaged. As the reinforcing material that can be used in this case, the same materials as those used in the conductive material can be used, and preferably acetylene black, ketjen black, talker black, activated carbon, graphite, carbon nanofiber, carbon nanotube, carbon A multi-branched carbon nanofiber in which protrusions mainly composed of carbon are grown from the surface of nanofiber (CNF) or a multi-branch carbon nanotube in which protrusions mainly composed of carbon are grown from the surface of carbon nanotube (CNT). More preferably, a multi-branched carbon nanofiber in which protrusions mainly composed of carbon are grown from the surface of carbon nanofiber (CNF) and a protrusion in which protrusions mainly composed of carbon are grown from the surface of carbon nanotube (CNT). Branched carbon nanochu It is. In particular, multi-branched carbon nanofibers / multi-branched carbon nanotubes have protrusions (three-dimensional) grown at an angle close to perpendicular to the fiber growth direction, unlike carbon fibers that do not grow normal protrusions. Therefore, when the electrode catalyst layer is transferred to the electrolyte membrane, it is possible to suppress biting into the membrane. Therefore, the electrode catalyst layer containing such a multi-branched carbon nanofiber / multi-branched carbon nanotube as a reinforcing material Is preferably used because it can maintain its structure better and can effectively prevent damage to the electrolyte membrane even when the catalyst layer is deformed due to deterioration or tightening pressure of the catalyst layer. . Under the present circumstances, the said reinforcing material may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture. The order of addition of the electrode catalyst, ion conductive material, solvent and filler in this case is not particularly limited, but (a) a step of adding and mixing the ion conductive material after mixing the electrode catalyst and filler; B) Steps of adding and mixing a filler after mixing the electrode catalyst and ion conductive material; (c) Steps of adding and mixing the electrode catalyst, ion conductive material and filler together Preferably used. At this time, the solvent may be added in any of the above portions.

  In the above method, the amount of the reinforcing material added when the reinforcing material is added to the catalyst ink is not particularly limited, but is preferably 0.01 to 0.4 with respect to 1 part by mass of the conductive material in the electrode catalyst. Part by mass. Within such a range, even after repeated normal start / stop / continuous operation, the structure of the catalyst layer can be sufficiently maintained and the diffusibility of the fuel gas can be maintained. Efficiency) can also be maintained. More preferably, the addition amount of the reinforcing material is 5 to 50% by mass, and most preferably 10 to 30% by mass with respect to the conductive material in the electrode catalyst.

  In the said method, it does not restrict | limit especially as a solvent, The normal solvent used for forming a catalyst layer can be used similarly. Specifically, lower alcohols such as water, cyclohexanol, ethanol, 1-propanol and 2-propanol can be used. Also, the amount of solvent used is not particularly limited, and the same amount as known can be used. In the catalyst ink, the electrode catalyst has a desired action, that is, hydrogen oxidation reaction (anode side) and oxygen reduction reaction. Any amount may be used as long as it can sufficiently exert the action of catalyzing (cathode side). It is preferable that the electrode catalyst is present in an amount such that it is 5 to 30% by mass, more preferably 9 to 20% by mass, based on the total mass of the catalyst ink.

  The catalyst ink of the present invention may contain a thickener. The use of a thickener is effective when the catalyst ink cannot be successfully applied onto a transfer mount. The thickener that can be used in this case is not particularly limited, and a known thickener can be used. Examples thereof include glycerin, ethylene glycol (EG), polyvinyl alcohol (PVA), and propylene glycol (PG). The amount of the thickener added when the thickener is used is not particularly limited as long as it does not interfere with the above effect of the present invention, but is preferably 5 to 20 with respect to the total mass of the catalyst ink. % By mass.

  Next, the anode and cathode catalyst inks prepared above (hereinafter collectively referred to as “catalyst inks”) are applied and dried on a transfer mount, respectively, so that the anode catalyst layer and the cathode catalyst are coated. Form a layer. In this case, as the transfer mount, a known sheet such as a PTFE (polytetrafluoroethylene) sheet, a PET (polyethylene terephthalate) sheet, or a polyester sheet can be used. The transfer mount is appropriately selected according to the type of catalyst ink to be used (particularly, a conductive material such as carbon in the ink). In the above step, the thickness of the catalyst layer is not particularly limited as long as it can sufficiently exhibit the catalytic action of the hydrogen oxidation reaction (anode side) and the oxygen reduction reaction (cathode side). Can be used. Specifically, the thickness of the catalyst layer is 1 to 30 μm, more preferably 1 to 20 μm. The method for applying the catalyst ink onto the transfer mount is not particularly limited, and a known method such as a screen printing method, a deposition method, or a spray method can be similarly applied. Also, the drying conditions of the applied catalyst layer are not particularly limited as long as the solvent can be completely removed from the catalyst layer. Specifically, the catalyst ink coating layer (catalyst layer) is dried in a vacuum dryer at room temperature to 100 ° C., more preferably 50 to 80 ° C., for 30 to 60 minutes. At this time, if the thickness of the catalyst layer is not sufficient, the coating and drying process is repeated until a desired thickness is obtained. Next, after sandwiching the electrolyte membrane with the catalyst layer thus produced, hot pressing is performed on the laminate. At this time, the hot press conditions are not particularly limited as long as the catalyst layer and the electrolyte membrane can be joined sufficiently closely, but are 100 to 200 ° C., more preferably 110 to 170 ° C., and 1 to 5 MPa with respect to the electrode surface. It is preferable to carry out at a pressing pressure of. Thereby, the bondability between the electrolyte membrane and the catalyst layer can be enhanced. After performing the hot pressing, the CCM comprising the catalyst layer and the electrolyte membrane can be obtained by removing the transfer mount.

  In the above description, the method for producing the CCM by performing the transfer method has been described. However, the CCM of the present invention may be produced by other methods such as direct coating. The production method in such a case is not particularly limited, and a known direct coating method can be used in the same manner or with appropriate modification. For example, the following methods can be used. Each catalyst layer is formed by directly applying the catalyst ink as described above onto the electrolyte membrane. At this time, the conditions for forming the cathode / anode catalyst layer on the electrolyte membrane are not particularly limited, and a known method can be used in the same manner or with appropriate modification. For example, the catalyst ink is applied on the electrolyte membrane so that the thickness after drying is 5 to 20 μm, and is 25 to 150 ° C., more preferably 60 to 120 ° C. in a vacuum dryer or under reduced pressure. Dry for 5 to 30 minutes, more preferably for 10 to 20 minutes. In addition, in the said process, when the thickness of a catalyst layer is not enough, the said application | coating and drying process is repeated until it becomes desired thickness.

  As will be described in detail below, the CCM according to the present invention may generally further include a gas diffusion layer. In this case, the gas diffusion layer is obtained by peeling off the transfer mount in the above method. It is preferable that the joined body is further sandwiched between gas diffusion layers to further join each catalyst layer after joining the catalyst layer and the electrolyte membrane. Alternatively, after the catalyst layer is formed on the surface of the gas diffusion layer in advance to produce the catalyst layer-gas diffusion layer assembly, the electrolyte membrane is heated with this catalyst layer-gas diffusion layer assembly in the same manner as described above. It is also preferable to sandwich and join by pressing.

  At this time, the gas diffusion layer used in the CCM is not particularly limited and can be used in the same manner. For example, the conductive and porous properties such as carbon woven fabric, paper-like paper body, felt, and non-woven fabric are used. The thing which uses the sheet-like material which has as a base material etc. are mentioned. The thickness of the substrate may be appropriately determined in consideration of the characteristics of the obtained gas diffusion layer, but may be about 30 to 500 μm. If the thickness is within the above range, sufficient mechanical strength and permeability such as gas and water can be achieved.

  The method for forming the catalyst layer on the surface of the gas diffusion layer is not particularly limited, and known methods such as a screen printing method, a deposition method, and a spray method can be similarly applied. Moreover, the formation conditions in particular on the gas diffusion layer surface of a catalyst layer are not restrict | limited, The conditions similar to the past can be applied with the above specific formation methods.

  The gas diffusion layer preferably contains a water repellent in the base material for the purpose of further improving water repellency and preventing a flooding phenomenon. Although it does not specifically limit as said water repellent, It is fluorine-type, such as a polytetrafluoroethylene (PTFE), a polyvinylidene fluoride (PVDF), a polyhexafluoropropylene, a tetrafluoroethylene-hexafluoropropylene copolymer (FEP). Examples thereof include polymer materials, polypropylene, and polyethylene.

  Moreover, in order to improve water repellency more, the said gas diffusion layer may have a carbon particle layer which consists of an aggregate | assembly of the carbon particle containing a water repellent on the said base material.

  The carbon particles are not particularly limited, and may be conventional ones such as carbon black, graphite, and expanded graphite. Of these, carbon blacks such as oil furnace black, channel black, lamp black, thermal black, and acetylene black are preferred because of their excellent electron conductivity and large specific surface area. The particle size of the carbon particles is preferably about 10 to 100 nm. Thereby, while being able to obtain the high drainage property by capillary force, it becomes possible to improve contact property with a catalyst layer.

  Examples of the water repellent used for the carbon particle layer include the same water repellents as those described above used for the substrate. Of these, fluorine-based polymer materials are preferably used because of their excellent water repellency and corrosion resistance during electrode reaction.

  In the carbon particle layer, the mixing ratio of the carbon particles to the water repellent may be insufficient to obtain water repellency as expected when there are too many carbon particles. If there are too many water repellents, sufficient electron conductivity may be obtained. There is a risk that it will not be obtained. Considering these, the mixing ratio of the carbon particles and the water repellent in the carbon particle layer is preferably about 90:10 to 40:60 in terms of mass ratio.

  The thickness of the carbon particle layer may be appropriately determined in consideration of the water repellency of the obtained gas diffusion layer.

  When a water repellent is contained in the gas diffusion layer, a general water repellent treatment method may be used. For example, after immersing the base material used for a gas diffusion layer in the dispersion liquid of a water repellent agent, the method of heat-drying with oven etc. is mentioned.

  When forming a carbon particle layer on a substrate in a gas diffusion layer, the carbon particles, water repellent, etc. are in a solvent such as water, alcohol solvents such as perfluorobenzene, dichloropentafluoropropane, methanol, ethanol, etc. A slurry is prepared by dispersing in a slurry, and the slurry is applied on a substrate and dried, or the slurry is dried and pulverized to form a powder, and this is applied to the gas diffusion layer. Use it. Then, it is preferable to heat-process at about 250-400 degreeC using a muffle furnace or a baking furnace.

  In addition, the manufacturing method of the joined body including the catalyst layer, the electrolyte membrane, and preferably the gas diffusion layer is not limited to the method described above. That is, a method in which a catalyst ink is applied and dried on an electrolyte membrane, followed by hot pressing, the catalyst layer is joined to the electrolyte membrane, and the obtained joined body is sandwiched between gas diffusion layers to form a CCM; May be applied and dried on the gas diffusion layer to form a catalyst layer, which may be joined to the electrolyte membrane by hot pressing, or any other known technique may be used as appropriate.

  As described above, the CCM of the present invention can suppress and prevent the catalyst layer from being thinned even after corrosion of the conductive material used as the catalyst carrier, particularly the carbon carrier. Further, in the CCM of the present invention, even if the conductive material is deteriorated / corroded, the gas flow path is secured by the filler, so that good diffusibility of the gas in the catalyst layer can be maintained. Therefore, the fuel cell having the electrolyte membrane-electrode assembly of the present invention can exhibit excellent power generation efficiency. Therefore, the present invention further provides a fuel cell using the CCM of the present invention.

  The type of the fuel cell is not particularly limited. In the above description, the polymer electrolyte fuel cell has been described as an example, but other than that, typical examples are an alkaline fuel cell and a phosphoric acid fuel cell. Examples thereof include an acid electrolyte fuel cell, a direct methanol fuel cell, and a micro fuel cell. Among these, a polymer electrolyte fuel cell is preferable because it is small in size, and can achieve high density and high output. The fuel cell is useful as a stationary power source in addition to a power source for a moving body such as a vehicle in which a mounting space is limited. However, the fuel cell is particularly useful for an automobile application in which system start / stop and output fluctuation frequently occur. It can be particularly preferably used.

  The polymer electrolyte fuel cell is useful as a power source for a moving body such as an automobile having a limited mounting space in addition to a stationary power source. In particular, moving bodies such as automobiles that are susceptible to corrosion of the carbon support due to the high output voltage required after a relatively long shutdown, and deterioration of the polymer electrolyte due to the high output voltage being taken out during operation. It is particularly preferred to be used as a power source.

  The configuration of the fuel cell is not particularly limited, and a conventionally known technique may be used as appropriate. Generally, the fuel cell has a structure in which a CCM is sandwiched between separators.

  The separator can be used without limitation as long as it is conventionally known, such as those made of carbon such as dense carbon graphite and a carbon plate, and those made of metal such as stainless steel. The separator has a function of separating air and fuel gas, and a channel groove for securing the channel may be formed. The thickness and size of the separator, the shape of the flow channel, and the like are not particularly limited, and may be appropriately determined in consideration of the output characteristics of the obtained fuel cell.

  Further, in order to prevent the gas supplied to each catalyst layer from leaking to the outside, a gas seal portion may be further provided at a portion where the catalyst layer is not formed on the gasket layer. Examples of the material constituting the gas seal portion include rubber materials such as fluoro rubber, silicon rubber, ethylene propylene rubber (EPDM), polyisobutylene rubber, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyhexafluoro. Fluorine polymer materials such as propylene, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and thermoplastic resins such as polyolefin and polyester. The thickness of the gas seal portion may be 2 mm to 50 μm, preferably about 1 mm to 100 μm.

  Further, a stack in which a plurality of CCMs are stacked via a separator and connected in series may be formed so that the fuel cell can obtain a desired voltage or the like. The shape of the fuel cell is not particularly limited, and may be determined as appropriate so that desired battery characteristics such as voltage can be obtained.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

Example 1
As a conductive material, 1 g of multi-branched carbon fiber (manufactured by Microphase: BET specific surface area 100 m 2 / g) is charged with 50 ml of ethanol as a reducing agent and 1000 g of a dinitrodiammine platinum nitrate aqueous solution having a platinum concentration of 0.1 wt% as a catalyst particle raw material. The mixture was stirred and mixed at 25 ° C. for 30 minutes, and then dispersed and mixed for another 30 minutes using an ultrasonic homogenizer. Thereafter, 10% CO gas was bubbled through the dispersion solution at 200 ml / min for 30 minutes, and then the dispersion solution was heated in a water bath while bubbling CO gas to 85 ° C. to 90 ° C. and then held for 2 hours. The reduction reaction was allowed to proceed until the liquid color became colorless and transparent, and then the resulting reaction liquid was filtered. The solid was separated and washed several times with pure water. Furthermore, it dried at 80 degreeC for 8 hours, and obtained Pt45wt%.

  A transmission electron microscope (TEM) image of the Pt-supported carbon powder (1) thus obtained was taken and shown in FIG.

Example 2
As a conductive material, 1 g of multi-branched carbon fiber (manufactured by Microphase: BET specific surface area of 100 m 2 / g), 50 ml of ethanol as a reducing agent, and 429 g of a dinitrodiammine platinum nitrate aqueous solution having a platinum concentration of 0.1 wt% as a catalyst particle material The mixture was stirred and mixed at 25 ° C. for 30 minutes, and then dispersed and mixed for another 30 minutes using an ultrasonic homogenizer. Thereafter, 10% CO gas was bubbled through the dispersion solution at 200 ml / min for 30 minutes, and then the dispersion solution was heated in a water bath while bubbling CO gas to 85 ° C. to 90 ° C. and then held for 2 hours. The reduction reaction was allowed to proceed until the liquid color became colorless and transparent, and then the resulting reaction liquid was filtered. The solid was separated and washed several times with pure water. Furthermore, it dried at 80 degreeC for 8 hours, and obtained Pt30 wt% carrying | support carbon powder (2).

Comparative Example 1
Carbon black (Ketjen Black EC manufactured by Ketjen Black International Co., Ltd .: BET specific surface area 800 m 2 / g) as a conductive material, 1 ml of ethanol as a reducing agent, and dinitrodiammine platinum having a platinum concentration of 0.1 wt% as a catalyst particle raw material After adding 1000 g of nitrate aqueous solution and stirring and mixing at 25 ° C. for 30 minutes, the mixture was dispersed and mixed for 30 minutes using an ultrasonic homogenizer. Thereafter, 10% CO gas was bubbled through the dispersion solution at 200 ml / min for 30 minutes, and then the dispersion solution was heated in a water bath while bubbling CO gas to 85 ° C. to 90 ° C. and then held for 2 hours. The reduction reaction was allowed to proceed until the liquid color became colorless and transparent, and then the resulting reaction liquid was filtered. The solid was separated and washed several times with pure water. Furthermore, it dried at 80 degreeC for 8 hours, and obtained Pt45wt% carrying | support carbon powder (3).

  A transmission electron microscope (TEM) image of the Pt-supported carbon powder (3) thus obtained is taken and shown in FIG.

Comparative Example 2
Carbon black (Ketjen Black EC manufactured by Ketjen Black International Co., Ltd .: BET specific surface area 800 m 2 / g) treated with high temperature and graphitized 1 g of graphitized Ketjen Black (conductive material) with 50 ml of ethanol as a reducing agent Then, 1000 g of a dinitrodiammine platinum nitrate aqueous solution having a platinum concentration of 0.1 wt% was added as a catalyst particle raw material, stirred and mixed at 25 ° C. for 30 minutes, and then dispersed and mixed for 30 minutes using an ultrasonic homogenizer. Thereafter, 10% CO gas was bubbled through the dispersion solution at 200 ml / min for 30 minutes, and then the dispersion solution was heated in a water bath while bubbling CO gas to 85 ° C. to 90 ° C. and then held for 2 hours. The reduction reaction was allowed to proceed until the liquid color became colorless and transparent, and then the resulting reaction liquid was filtered. The solid was separated and washed several times with pure water. Furthermore, it dried at 80 degreeC for 8 hours, and Pt45 wt% carrying | support carbon powder (4) was obtained.

  A transmission electron microscope (TEM) image of the Pt-supported carbon powder (4) thus obtained was taken and shown in FIG.

Example 3: Carbon corrosion resistance evaluation (high potential test) (ECA after holding for 25 minutes / initial ECA)
The carbon corrosion resistance of the carbon powders obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was evaluated according to the following method. The results are shown in Table 1 below.

<Corrosion resistance evaluation method>
A gold wire coil having a diameter of 0.5 mm was prepared, and the coil was immersed in catalyst ink, and then dried under reduced pressure at room temperature for 10 minutes. After drying under reduced pressure, the sample was further dried at 80 ° C. under atmospheric pressure for 3 hours to obtain an evaluation sample. For the measurement, a three-electrode electrochemical evaluation cell was used. A hydrogen electrode was used as the reference electrode, and a platinum wire coil was attached to the counter electrode. The evaluation sample produced by the above procedure was attached to the working electrode, and a 0.5 N molar aqueous sulfuric acid solution was used as the electrolyte. The high potential corrosion test was performed at room temperature with an applied voltage of 1.6 V (vs SHE), and CV was measured after 25 minutes. The sweep voltage range during CV measurement was -0.02 V to 1.15 V (vs SHE), and the sweep speed was 50 mV / sec. Moreover, the measurement was implemented at 70 degreeC. After CV measurement, ECA (effective surface area) was calculated from the CV diagram, and after holding for 25 minutes, carbon corrosion resistance was evaluated by ECA / initial ECA.

  From Table 1 above, the electrode catalyst of the present invention exhibits significantly higher carbon corrosion resistance than the electrode catalyst of the comparative example in which the dispersion state of the catalyst particles on the conductive material does not satisfy the conditions according to the present invention. I understand. The “fuel temperature of the conductive carrier” in Table 1 below indicates the combustion temperature of the conductive material due to the glass transition temperature (TG), and the carbon carrier (that is, the conductive material itself before supporting the electrode catalyst). Used as an indicator of corrosion resistance (oxidation resistance). At this time, a high combustion temperature means that the carbon carrier is excellent in corrosion resistance (oxidation resistance). Therefore, as is apparent from Table 1, in Comparative Examples 1 and 2, compared with Examples 1 and 2, the carbon support having excellent corrosion resistance was used as the conductive material. It is shown that the electrode catalysts of Examples 1 and 2 using a carbon support having inferior corrosion resistance have improved carbon corrosion resistance. From this, optimizing the supported state of the catalyst particles on the conductive material as in the present invention is extremely effective in improving the carbon corrosion resistance, and hence obtaining an electrode catalyst having excellent durability and high catalytic activity over a long period of time. It is considered to be an important factor.

  The electrode catalyst of the present invention is particularly useful as an electrode catalyst for polymer fuel cells because it is excellent in the corrosion resistance of conductive materials.

It is a figure which shows the support state of the catalyst component carry | supported by the electroconductive material in the conventional electrode catalyst. It is a figure which shows the support state of the catalyst component carry | supported by the electroconductive material in the conventional electrode catalyst. It is a figure which shows the support state of the catalyst component carry | supported by the electroconductive material in the electrode catalyst of this invention. In the electrode catalyst of this invention, it is a figure for demonstrating "the distance of each gravity center of three or more adjacent catalyst particles, and the gravity center of the catalyst particle A". It is the figure which plotted S1 (m < 2 > / g) (vertical axis) with respect to average particle diameter X (nm) (horizontal axis). In the electrode catalyst of this invention, it is a figure explaining the catalyst layer which uses carbon nanofiber / carbon nanotube and multi-branch carbon nanofiber / multi-branch carbon nanotube as an electroconductive material. It is a figure which shows the support state which the catalyst which has water electrolysis activity in the electrode catalyst of this invention, and a catalyst particle co-supported on an electroconductive material. 2 is a transmission electron microscope (TEM) image of the Pt-supported carbon powder (1) obtained in Example 1. FIG. 2 is a transmission electron microscope (TEM) image of the Pt-supported carbon powder (3) obtained in Comparative Example 1. 4 is a transmission electron microscope (TEM) image of the Pt-supported carbon powder (4) obtained in Comparative Example 2.

Claims (16)

  1. In an electrode catalyst in which catalyst particles are supported on a conductive material, when the average particle diameter of the catalyst particles supported on the conductive material is X, three or more catalysts adjacent to any given catalyst particle A The catalyst particles are supported on the conductive material such that the center of gravity of each of the particles is in the range of a distance of 0.5X to 2X from the center of gravity of the catalyst particle A,
    The catalyst particles are platinum particles or 30 to 90 atomic% of platinum and at least one alloying metal 10 selected from the group consisting of palladium, rhodium, ruthenium, iridium, cobalt, nickel, iron, chromium, and manganese. A multi-branched carbon nanofiber or carbon nanotube (CNT) formed from an alloy having a composition of ˜70 atomic%, and the conductive material is a carbon nanofiber (CNF) having a carbon-based protrusion grown on the surface thereof. electrode catalyst, wherein the at least one der Turkey from the surface of the multi-vessel carbon nanotubes are grown protrusion composed mainly of carbon.
  2.   When the average particle diameter of the catalyst particles carried on the conductive material is X and the catalyst particles are assumed to be spherical with a diameter X, the area S1 where the catalyst particles occupy the conductive material and the conductivity per gram. The surface area S2 of the material (where S2 excludes the surface area in the pores having a pore diameter X or less), the mass fraction G1 of the catalyst component in the electrode catalyst, and the mass fraction G2 of the conductive material in the electrode catalyst The electrode catalyst according to claim 1, which satisfies the following formula: (S1 · G1) / (S2 · G2) = 0.2 to 1.35.
  3.   The electrode catalyst according to claim 1 or 2, wherein an average particle diameter X of the catalyst particles supported on the conductive material is in the range of 1 nm to 10 nm.
  4.   The electrode catalyst according to any one of claims 1 to 3, wherein a particle size of catalyst particles supported on the conductive material is in a range of 0.75X to 1.5X.
  5. The electrode catalyst according to any one of claims 1 to 4 , wherein the electrode catalyst is produced by supporting a catalyst component on a conductive material using a solution reduction method.
  6. In the step of supporting the catalyst component on the conductive material using the solution reduction method, at least one selected from the group consisting of ethanol, methanol, propanol, formic acid, formaldehyde, sodium thiosulfate, citric acid, sodium borohydride, and hydrazine. The electrocatalyst according to claim 5 , wherein the seed is used as a reducing agent for the catalyst particles.
  7. The electrode catalyst according to claim 6 , wherein carbon monoxide gas is introduced when the catalyst component is reduced with a reducing agent in the step of supporting the catalyst component on the conductive material using a solution reduction method.
  8. Catalyst having a water electrolysis activity was further co-supported with the catalyst particles to the conductive material, the catalyst having the water electrolysis activity is formed by a different component than the catalyst particles, any of claims 1-7 1 The electrode catalyst according to item.
  9. The electrode catalyst according to claim 8 , wherein the catalyst having water electrolysis activity is formed from at least one of iridium oxide, ruthenium oxide, iridium, or ruthenium.
  10. The electrode catalyst according to claim 8 or 9 , wherein the catalyst having water electrolysis activity is supported on the conductive material together with the catalyst particles by a heating oxidation method or an electrodeposition method.
  11. 2. An electrolyte membrane-electrode assembly comprising an electrolyte membrane, a cathode catalyst layer disposed on one side of the electrolyte membrane, and an anode catalyst layer disposed on the other side of the electrolyte membrane, 10. An electrolyte membrane-electrode assembly, wherein the electrode catalyst according to any one of 10 to 10 is used in at least one of a cathode catalyst layer and an anode catalyst layer.
  12. The electrolyte membrane-electrode assembly according to claim 11 , wherein at least one of the cathode catalyst layer and the anode catalyst layer further contains a reinforcing material.
  13. The electrolyte membrane-electrode junction according to claim 12 , wherein the reinforcing material is at least one selected from the group consisting of acetylene black, ketjen black, talker black, activated carbon, graphite, carbon nanofibers, and carbon nanotubes. body.
  14. In the reinforcing material, protrusions mainly composed of carbon are grown from the surface of multi-branched carbon nanofibers or carbon nanotubes (CNT) in which protrusions mainly composed of carbon are grown from the surface of carbon nanofibers (CNF). The electrolyte membrane-electrode assembly according to claim 12 or 13 , comprising at least one of multi-branched carbon nanotubes.
  15. The electrolyte membrane according to any one of claims 12 to 14 , wherein the addition amount of the reinforcing material is 0.01 to 0.4 parts by mass with respect to 1 part by mass of the conductive material in the electrode catalyst. Electrode assembly.
  16. A fuel cell comprising the electrolyte membrane-electrode assembly according to any one of claims 12 to 15 .
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JP5581884B2 (en) * 2010-08-06 2014-09-03 株式会社Gsユアサ Method for producing catalyst-supported powder for fuel cell, method for producing electrode for fuel cell
JP5758609B2 (en) * 2010-11-05 2015-08-05 公立大学法人大阪府立大学 Method for producing core-shell particles
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JP5755124B2 (en) * 2011-12-01 2015-07-29 株式会社キャタラー Method for producing cathode catalyst for polymer electrolyte fuel cell
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