WO2005083818A1 - Catalyseur d'électrode pour pile à combustible et pile à combustible utilisant ce dernier - Google Patents

Catalyseur d'électrode pour pile à combustible et pile à combustible utilisant ce dernier Download PDF

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WO2005083818A1
WO2005083818A1 PCT/JP2005/002810 JP2005002810W WO2005083818A1 WO 2005083818 A1 WO2005083818 A1 WO 2005083818A1 JP 2005002810 W JP2005002810 W JP 2005002810W WO 2005083818 A1 WO2005083818 A1 WO 2005083818A1
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Prior art keywords
carrier
catalyst
fuel cell
carbon
specific surface
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PCT/JP2005/002810
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English (en)
Japanese (ja)
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Hirotaka Mizuhata
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Sharp Kabushiki Kaisha
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Priority to JP2006510422A priority Critical patent/JP4759507B2/ja
Publication of WO2005083818A1 publication Critical patent/WO2005083818A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • Electrode catalyst for fuel cell fuel cell using the same
  • the present invention relates to a fuel cell electrode catalyst and a fuel cell using the same.
  • Solid polymer electrolyte fuel cells are capable of providing high current densities at low temperatures, and are therefore being developed as power supplies for portable devices, driving power supplies for automobiles, and power supplies for cogeneration.
  • a solid polymer electrolyte fuel cell basically has a layer structure in which a solid polymer electrolyte membrane is disposed between a fuel electrode (anode) and an air electrode (force sword).
  • a fuel electrode anode
  • an air electrode force sword
  • the fuel electrode 2H ⁇ 4H + + 4e
  • Air electrode O + 4H + + 4e— ⁇ 2H ⁇
  • Air electrode 3 / 2 ⁇ + 6H + + 6e + ⁇ 3H O
  • Both the fuel electrode and the air electrode in the solid polymer electrolyte fuel cell have a catalyst-supporting carbon carrier in which a catalyst metal such as platinum is highly dispersed on a carbon carrier in order to obtain the three-phase interface described above.
  • a PTFE (polytetrafluoroethylene) particle-dispersed solution applied to a polymer film or a conductive porous carbon electrode substrate, heated and dried to form a film. Coating, impregnating and drying after this, or the above-mentioned catalyst-supporting carbon carrier and ion exchange resin solution and, if necessary,
  • Replacement form (Rule 26) It is produced by a method of forming a paste comprising PTFE particles on a polymer film or a conductive porous body on a carbon electrode substrate and then drying.
  • the catalyst metal supported on the carbon support has a small effective ratio at the time of the reaction, and has a low activity in the electrode reaction. .
  • the conventional manufacturing method uses a method in which a catalyst metal is previously supported on a carbon carrier, and then the catalyst-supporting carbon carrier and an ion exchange resin are mixed.
  • Non-Patent Document 1 That is, as described in Non-Patent Document 1, the ion exchange resin cannot be distributed inside the fine pores in the carbon support because of its large molecule. The catalyst metal supported in the pores does not contact the ion exchange resin. As explained above, since the electrochemical reaction proceeds only at the three-phase interface, catalytic metals that do not come into contact with the ion exchange resin do not contribute to the reaction.
  • FIG. 5 and paragraph 25 of Patent Document 2 show that while the specific surface area of the carrier is small, the current value obtained as the specific surface area of the carrier increases is increased to 800 m 2. It is described that, when it exceeds / g, the obtained current value decreases as the specific surface area of the support increases. Therefore, there is a limit to improving the performance of the catalyst and further the fuel cell simply by increasing the specific surface area of the carrier.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 9-167622
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2000-100448
  • Non-Patent Document 1 J. Electrochem. So, 142 (1995) 4143
  • the present invention has been made in view of the above circumstances, and provides an electrode catalyst for a fuel cell capable of obtaining high performance.
  • the fuel cell electrode catalyst of the present invention includes a support and a catalyst metal supported on the support.
  • the support has a surface modified with a proton-dissociable functional group, and has a specific surface area by a BET method. 2170 m 2 / g.
  • the specific surface area of the support was 800 m 2 / g or more
  • the performance of the catalyst was reduced as the specific surface area of the support was increased.
  • the reasons are considered as follows.
  • the fuel cell electrode catalyst is usually used by being mixed with an ion exchange resin.
  • the carrier supporting the catalytic metal usually has minute pores of various sizes (when the carrier is composed of aggregates of minute particles, the term “fine pores” means the inside of the aggregate. Space.).
  • fine pores means the inside of the aggregate. Space.
  • Increasing the specific surface area of the support increases the proportion of pores that are so small that the ion exchange resin cannot enter. When the catalyst metal is carried in such small pores, the catalyst metal cannot contact the ion exchange resin. Therefore, the ability to transport the protons produced by the reaction does not work, and as a result, the catalytic metal cannot exhibit its performance. Therefore, the performance of the catalyst decreases.
  • the inventor of the present invention has found that, by modifying the surface of a carrier with a proton-dissociating functional group, proton transport in the micropores of the carrier is promoted, and the above problem is improved. Issued. Then, the inventor can use a carrier having a specific surface area of 900 m 2 / g or more, and by modifying the surface of the carrier with a proton dissociating functional group, it is possible to highly disperse the catalyst metal S. And found that the performance of each catalyst metal can be improved. . Furthermore, the inventors have found that when the specific surface area of the support exceeds 2170 m 2 / g, the performance of the catalyst is reduced even in the case of the present invention.
  • the inventor has proposed that a catalyst metal is supported on a carrier having a specific surface area of 900 to 2170 m 2 / g, and that the surface of the carrier is modified with a proton dissociating functional group.
  • the present inventors have found that an electrode catalyst for a fuel cell having high performance can be obtained, and have completed the present invention.
  • an electrode catalyst for a fuel cell having high performance can be obtained. Therefore, a fuel cell having high performance can be manufactured by using the catalyst of the present invention.
  • the catalyst metal can be highly dispersed, and as a result, the utilization efficiency of the catalyst metal is improved. Therefore, the amount of the catalyst metal (often made of an expensive noble metal) can be reduced, and the fuel cell electrode catalyst can be manufactured at low cost.
  • the area of a site where a chemical reaction occurs can be increased.
  • current can be taken out at a high current density without deteriorating performance. Therefore, it can be used for devices that require high current density, such as fuel cells for automobiles and fuel cells for portable devices.
  • FIG. 1 is a graph showing the relationship between the specific surface area of the carbon support and the current density according to Example 1 and Comparative Examples 1 and 2.
  • FIG. 2 is a graph showing a relationship between an interlayer distance of a carbon carrier and a current density according to Example 2 and Comparative Example 3.
  • FIG. 3 is a graph showing the relationship between the specific surface area and interlayer distance of the carbon support and the current density according to Examples 3 and 4 and Comparative Examples 4 and 5.
  • FIG. 4 is a graph showing the relationship between the specific surface area of the carbon support and the particle size of the supported platinum according to Experimental Examples 1 and 2.
  • FIG. 5 is a graph showing the relationship between the specific surface area of the carbon support and the current density according to Experimental Examples 1 and 2.
  • FIG. 6 is a graph showing the relationship between the interlayer distance of the carbon support and the current density according to Experimental Example 3. is there.
  • FIG. 7 is a graph showing the relationship between the specific surface area of a carbon support and the particle size of a supported PtRu alloy according to Experimental Examples 4 and 5.
  • FIG. 8 is a graph showing the relationship between the specific surface area of the carbon support and the current density according to Experimental Examples 4 and 5.
  • the fuel cell electrode catalyst of the present invention comprises a support and a catalyst metal supported on the support.
  • the support has a surface modified with a proton dissociating functional group, and a specific surface area by a BET method. S900—2170 m 2 / g.
  • the fuel cell electrode catalyst of the present invention has, for example, (1) a specific surface area of 90 according to the BET method.
  • a catalyst metal is supported on a carrier of 0 to 2170 m 2 / g, and (2) a step of modifying the surface of the carrier with a proton-dissociable functional group.
  • the carrier is preferably made of a conductive material. This is because electrons generated by the reaction on the catalyst metal supported on the carrier are efficiently transmitted.
  • the carrier is not particularly limited as long as it does not adversely affect the reaction on the catalyst metal.
  • Representative carriers include carbon materials commonly used in the art.
  • the raw material of carbon material is Examples include crude oil products or vegetable oils such as coconut oil.
  • the carrier may be, for example, a metal material such as gold, silver, titanium or niobium; a semiconductor material such as silicon (n-type, p-type or doped); carbon black such as furnace black or activated carbon; It is made of fiber, carbon material such as multi-walled carbon nanotube or nanocarbon.
  • the carrier may be made of an insulating material or a semiconductive material.
  • a carrier supporting a catalyst metal and the above-described conductive material are mixed and used.
  • the carrier is made of a metal oxide such as silica as an insulating material, and made of (doped) silicon as a semiconductive material.
  • the carrier preferably comprises an aggregate of fine particles.
  • the specific surface area of the carrier becomes large, and it is easy to achieve a large specific surface area described later.
  • the diameter of the fine particles is preferably about 10 to 30 nm, and the diameter of the aggregate is preferably about several hundreds and several ⁇ m.
  • the carrier has a specific surface area force of 900-2170 m 2 / g by the BET method. This is because when the specific surface area of the support is 900 m 2 / g or more, the catalyst performance can be greatly improved by modifying the surface of the support with a proton-dissociable functional group. On the other hand, when the specific surface area exceeds 217 Om 2 / g, the catalytic performance decreases. This is considered to be because in this case, the electric resistance of the carrier increases, and the efficiency of the electron transfer decreases.
  • the carrier preferably has a specific surface area of 1000 to 1800 m 2 / g.
  • the particle diameter of the supported catalyst particles is not sufficiently small, and if it is larger than 1800 m 2 / g, the effective diffusion path of a reactant such as hydrogen or methanol becomes longer, This is because it is considered that the phenomenon of the rate of material supply is likely to occur (in this case, the battery characteristics at high current density are reduced).
  • the specific surface area of the carrier is more preferably 1200 1600 m 2 / g.
  • the specific surface area is measured using the BET method. In the examples of the present invention, the specific surface area was measured using a model BELSORP18 manufactured by Bell Japan.
  • the carrier may be a commercially available one, or may be manufactured by a known method.
  • An example of a commercially available carrier is BP_2000 (Carbon Black) Power S manufactured by Cabot.
  • the specific surface area of this carrier is 1475 m 2 / g, which is included in the above range.
  • the specific surface area of a commercially available carrier may be adjusted by subjecting the carrier to physical or chemical treatment. For example, by performing liquid phase oxidation treatment or water vapor treatment on the carrier, the specific surface area of the carrier can be increased. These methods are particularly effective for carbon carriers.
  • a catalytic metal is supported on a support.
  • the catalyst metal is preferably made of a platinum group metal such as platinum, ruthenium, rhodium, indium, palladium or osmium, or an alloy thereof.
  • the catalyst metal is an alloy containing at least one element selected from the group consisting of magnesium, aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, steel, zinc, silver and tungsten, and a platinum group metal. preferable.
  • the catalyst metal is preferably dispersed in the form of particles on a carrier.
  • the catalyst metal can be supported on the carrier by, for example, mixing a complex containing the catalyst metal and the carrier and reducing the complex containing the catalyst metal in that state.
  • the amount of the supported catalyst metal can be changed. It is preferable that the catalyst metal is supported on the support so that the loading amount is 5 to 70% by weight. If the amount is less than 5% by weight, the amount of the catalyst metal to be carried is too small, and a sufficient catalyst area cannot be secured, thereby deteriorating the electrode performance. Since the diameter of the catalyst tends to increase, the catalytic activity per unit mass of the catalyst decreases, and the electrode performance decreases.
  • the ⁇ supported amount '' means a value obtained by dividing the weight of the supported catalyst metal by the weight of the carrier after supporting the catalyst metal (that is, the total weight of the carrier and the catalyst metal). I do.
  • the weight of the supported catalyst metal can be determined by removing the carbon by combustion and measuring the remaining weight.
  • the surface of the support is modified with a proton-dissociable functional group.
  • Proton dissociative functionality The group preferably comprises at least one selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group, and particularly preferably comprises a sulfonic acid group. This is because the sulfonate group can be introduced into the carrier by a general organic chemical reaction.
  • the sulfonating agent for example, sulfuric acid, fuming sulfuric acid, sulfur trioxide, sulfuric acid sulfuric acid, or phenolic sulfuric acid can be used.
  • the carrier Before the modification with the proton dissociating functional group, the carrier is preferably subjected to a surface treatment such as an ozone treatment, a plasma treatment, a liquid phase oxidation treatment, a steam treatment or a fluorine treatment. Thereby, a reactive group such as a hydroxyl group is formed on the carrier. Then, the proton dissociable functional group can be easily introduced onto the carrier through a chemical reaction between the reactive group and an organic compound containing a proton dissociable functional group. Further, by controlling the degree of the surface treatment, the density at which the reactive groups are formed can be controlled, and therefore, the density of the proton-dissociable functional groups on the carrier can be controlled. This makes it possible to easily introduce a proton dissociable functional group at a required density on the support, and to obtain a high-performance and high-performance catalyst.
  • a surface treatment such as an ozone treatment, a plasma treatment, a liquid phase oxidation treatment, a steam treatment or a fluorine treatment.
  • the density of the proton dissociable functional groups on the carbon support can be controlled by controlling the degree of graphitization of the carbon support.
  • the principle is considered as follows.
  • the degree of graphitization of the carbon carrier is high, the number of sites having high reaction activity is small, and it is difficult to introduce a proton dissociable functional group.
  • the degree of graphitization of the carbon carrier is low, the proton-dissociable functional group is likely to be introduced because the number of sites having high reaction activity is large.
  • the degree of graphitization of the carbon support the density of the proton dissociable functional groups on the carbon support can be controlled.
  • the degree of graphitization of the carbon support can be increased, for example, by performing a heat treatment at 1600 to 2000 ° C for about 30 minutes in an inert gas.
  • the degree of graphitization of the carbon carrier can be reduced by, for example, performing liquid phase oxidation treatment or steam treatment.
  • the degree of graphitization of the carbon support is determined by the average lattice spacing of the [002] plane (hereinafter referred to as "interlayer distance"). That's it. ).
  • the interlayer distance of the carbon support is the plane spacing of the hexagonal mesh based on the graphite structure of the carbon support, and is calculated from the X-ray diffraction pattern. Specifically, it can be calculated based on the Bragg equation using a powder X-ray diffractometer. Incidentally, the interlayer distance of the complete graphite crystal is 0.3345 nm. Therefore, the closer to this value, the higher the degree of graphitization.
  • the carbon carrier preferably has an interlayer distance of 0.35-0.388 nm.
  • the degree of graphitization of the carbon carrier is high, and the reactivity with the surface treating agent is low. Therefore, since the amount of proton dissociable functional groups that can be introduced through the above reaction decreases, a sufficient proton diffusion layer cannot be formed, and the electrode activity decreases.
  • it exceeds 0.388 nm the degree of graphitization is too low, the electron conductivity decreases, and the electrode activity tends to decrease.
  • the fuel cell of the present invention includes an electrolyte layer and a pair of electrodes sandwiching the electrolyte layer, and at least one of the electrodes includes the catalyst.
  • the electrolyte layer is made of a solid polymer or phosphoric acid.
  • a fuel cell is a solid polymer electrolyte fuel cell.
  • a fuel cell is a phosphoric acid fuel cell.
  • the electrode comprises the catalyst described above. Also, the electrode preferably comprises a catalyst mixed with an ion exchange resin.
  • the electrode can be formed, for example, by dispersing the above catalyst in an ion exchange resin dispersion solution and applying the obtained solution on carbon paper or the like.
  • Fuel cells were prepared using carriers having various specific surface areas and interlayer distances by the method described below, and the current density was measured.
  • the carbon carrier carrying platinum was suspended in a dichloromethane solution containing 2 (4-chlorosulfurphenyl) ethyltrichlorosilane, and the suspension was stirred at room temperature for 2 hours. Next, it was filtered and dried under reduced pressure to obtain a carbon carrier catalyst modified with a proton dissociable functional group.
  • the resulting carbon supported catalyst was immersed in 5 wt / ⁇ 01 1 (R) dispersion solution to prepare a paste dispersed by sonication. This was coated on carbon paper (Toray Co., Ltd., TPG-H-060) to produce a fuel cell electrode having a catalyst layer formed thereon, and this electrode was used for ion exchange membrane Nafion (registered trademark) manufactured by DuPont. ) A membrane (model N-117) was sandwiched and integrated to obtain a fuel cell according to this example.
  • a fuel cell was manufactured in the same manner as in Example 1 except that the carbon supports F, G, H, and I shown in Table 1 were used as supports. 1-3. Production of Fuel Cell According to Comparative Example 2
  • a fuel cell was manufactured in the same manner as in Example 1, except that the step of modifying the carbon support AI with the proton-dissociable functional group was not performed.
  • Example 1 The fuel cells obtained in Example 1 and Comparative Examples 1 and 2 were subjected to a power generation test by supplying humidified hydrogen to the anode side and humidified air to the power source side.
  • Figure 1 shows the results.
  • FIG. 1 shows the relationship between the specific surface area of the carbon support and the current density when the battery voltage becomes S900 mV after correcting the ohmic resistance. It is considered that the magnitude of the current density when the battery voltage reaches 900 mV is correlated with the magnitude of the current density in the reaction-controlled state, in other words, the magnitude of the three-phase interface.
  • reference numeral 1 indicates data on Example 1
  • reference numeral 3 indicates data on Comparative Example 1
  • reference numeral 5 indicates data on Comparative Example 2.
  • the value of the current density is obtained when the carbon carrier does not have a proton dissociating functional group (Comparative Example 1).
  • the force showing the high current density is higher than the specific surface area of the carbon support.
  • a fuel cell was manufactured in the same manner as in Example 1 using the carbon supports J, K, and L shown in Table 2 as supports.
  • a fuel cell was manufactured in the same manner as in Example 1 except that the step of modifying the carbon support J-L was not performed with the step of modifying with a proton-dissociable functional group.
  • Example 2 The fuel cells obtained in Example 2 and Comparative Example 3 were subjected to a power generation test by supplying humidified hydrogen to the anode side and humidified air to the force side.
  • Figure 2 shows the results.
  • FIG. 2 shows the relationship between the interlayer distance of the carbon carrier and the current density when the battery voltage corrected for the ohmic resistance becomes 500 mV.
  • the magnitude of the current density when the battery voltage becomes 500 mV is considered to be the magnitude of the current density in the diffusion-controlled state, that is, the current density in the state where the effect of electron conduction and proton conduction in the catalyst layer appears.
  • reference numeral 7 indicates data on Example 2
  • reference numeral 9 indicates data on Comparative Example 3.
  • the value of the current density when the carbon support has a proton dissociative functional group is as follows. It can be seen that a higher current density is shown when compared with the value of the current density in the case where no dissociative functional group is present (Comparative Example 3). These results were obtained when the interlayer distance was about 0.35 to 0.388 nm, the density of proton dissociable functional groups on the carbon support was sufficiently high, and the conductivity of the carbon support was high. Is enough It is thought that this is because it became higher.
  • Fuel cells were prepared using carriers having various specific surface areas and interlayer distances by the following method, and the power density was measured.
  • Example 3 as a carrier having a specific surface area of 900 2170 m 2 / g and an interlayer distance force of carbon carrier of 0.350 0.388 nm, M, N, 0, P, Q, and A fuel cell was manufactured in the same manner as in Example 1 using an (R, S, TO) carbon carrier.
  • Example 3 As a carbon support having an interlayer foot separation in the range of 0.35-0.388 nm and not satisfying the condition of a specific surface area of 900-2170 m 2 / g, the carbon support of X, Y, and ⁇ shown in Table 3 was used. Using this, a fuel cell was manufactured in the same manner as in Example 1.
  • carbon supports a, b, and c shown in Table 3 were used as a carbon support that does not satisfy any of the conditions of specific surface area 900-2170 m 2 / g and interlayer distance 0.35-0.388 nm.
  • a fuel cell was manufactured in the same manner.
  • Example 3 The fuel cells obtained in Examples 3 and 4 and Comparative Examples 4 and 5 were subjected to a power generation test by supplying humidified hydrogen to the anode side and humidified air to the power source side.
  • the results are shown in Table 3 and FIG. Table 3 shows the current density at the output density when the current density was 800 mA m 2 .
  • FIG. 3 is a diagram showing the relationship between the specific surface area and interlayer distance of the carbon support and the output density when the current density is 800 mA / cm 2 .
  • Example 3 in which both the specific surface area and the interlayer distance are satisfied, a higher output density can be obtained as compared with Example 4, in which at least one of the conditions does not satisfy the conditions, and Comparative Examples 4 and 5.
  • the surface of the carbon support was modified with a proton dissociating functional group, and the surface area force of the carbon support was S900—2170 m 2 / g. At 388 mn, it was found that particularly high power density was obtained.
  • the carbon carrier carrying platinum was suspended in a dichloromethane solution containing 2 (4-chlorosulfurphenyl) ethyltrichlorosilane, and the suspension was stirred at room temperature for 2 hours. Next, it was filtered and dried under reduced pressure to obtain a carbon carrier catalyst modified with a proton dissociable functional group.
  • the resulting carbon supported catalyst was immersed in 5 wt / ⁇ 01 1 (R) dispersion solution to prepare a paste dispersed by sonication. This was coated on carbon paper (Toray Co., Ltd., TPG-H-060) to produce a fuel cell electrode having a catalyst layer formed thereon, and this electrode was used for ion exchange membrane Nafion (registered trademark) manufactured by DuPont. ) A membrane (model N-117) was sandwiched and integrated to obtain a fuel cell according to this experimental example.
  • a fuel cell was manufactured in the same manner as in Experimental Example 1, except that the step of modifying the carbon support XI-X7 with a proton-dissociable functional group was not performed.
  • the particle size of the platinum supported on the carbon support XI X7 was measured.
  • Figure 4 shows the results.
  • the platinum particle size was calculated based on the Schiller equation using a powder X-ray diffractometer. According to FIG. 4, the larger the specific surface area, the smaller the platinum particle size. This indicates that the higher the specific surface area, the more highly the platinum is dispersed.
  • FIG. 5 shows the relationship between the specific surface area of the carbon carrier and the current density when the battery voltage corrected for ohmic resistance is 900 mV.
  • the magnitude of the current density when the battery voltage reaches 900 mV is considered to be correlated with the magnitude of the current density in the reaction-controlled state, in other words, the magnitude of the three-phase interface.
  • reference numeral 55 indicates data on Experimental Example 1
  • reference numeral 57 indicates data on Experimental Example 2.
  • the specific surface area exceeds 900 m 2 / g
  • the case where the carbon carrier has a proton dissociating functional group is more than the case where it does not have it (Experimental Example 2).
  • the current density has increased.
  • the specific surface area is 2170 m 2 / g
  • the current density is higher in Experimental Example 1 than in Experimental Example 2. Therefore, it was found that a high current density was obtained when the surface of the carbon support was modified with a proton dissociating functional group and the specific surface area of the carbon support was 900-2170 m 2 / g.
  • Figure 6 shows the relationship between the interlayer distance (average lattice spacing of the [002] plane of the carbon support) and the current density. It is a graph which shows a relationship. Since the specific surface areas of the carbon supports X8 to X10 are close to each other, it is considered that the difference in current density reflects the difference in interlayer distance, that is, the difference in the degree of graphitization of the carbon support. Further, as described above, the degree of graphitization of the carbon support correlates with the density of the proton dissociable functional groups on the carbon support.
  • a fuel cell was manufactured by the following method using a carbon carrier XI X7 as a carrier.
  • the carbon support supporting the above catalyst was suspended in a 5% by weight sulfur trioxide solution (solvent: N, N-dimethylacetamide) and stirred at 120 ° C. for 4 hours.
  • the resultant was filtered and dried under reduced pressure to obtain a carbon carrier catalyst modified with a proton dissociable functional group.
  • the obtained carbon carrier catalyst was immersed in a 5% by weight / ⁇ 011 (registered trademark) dispersion solution and dispersed by ultrasonic treatment to prepare a paste. This was coated on carbon paper (Toray's TPG_H_060) to form a fuel cell electrode with a catalyst layer formed.
  • the fuel cell according to the present experimental example was obtained by integrating the electrode with a Nafion (registered trademark) membrane (model N-117), which is an ion exchange membrane manufactured by DuPont.
  • a fuel cell was manufactured in the same manner as in Experimental Example 4, except that the step of modifying the carbon support XI X7 with a proton-dissociable functional group was not performed.
  • FIG. 7 shows that the larger the specific surface area, the smaller the PtRu alloy particle size. This indicates that as the specific surface area increases, the PtRu alloy is more highly dispersed.
  • FIG. 8 shows the results.
  • FIG. 8 shows the relationship between the specific surface area of the carbon support and the current density when the battery voltage with the corrected ohmic resistance becomes 500 mV.
  • reference numeral 65 indicates data on Experimental Example 4
  • reference numeral 67 indicates data on Experimental Example 5.
  • the specific surface area exceeds 900 m 2 / g
  • the case where the carbon carrier has a proton dissociating functional group is less than that of the case (Experimental Example 5). It can be seen that the current density is higher than in ()). Also, even when the specific surface area is 2170 m 2 / g, it can be seen that the current density is higher in Experimental Example 4 than in Experimental Example 5. Therefore, it was found that a high current density was obtained when the surface of the carbon support was modified with a proton dissociating functional group and the specific surface area of the carbon support was 900-2170 m 2 / g.

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Abstract

Il est divulgué un catalyseur d'électrode pour piles à combustible faisant preuve d'un bon rendement. Le catalyseur d'électrode pour piles à combustible comprend un substrat et un métal catalyseur supporté par le substrat. La surface du substrat est modifiée avec un groupe fonctionnel à dissociation de protons et a une zone de surface spécifique BET comprise entre 900 et 2170 m2/g.
PCT/JP2005/002810 2004-02-26 2005-02-22 Catalyseur d'électrode pour pile à combustible et pile à combustible utilisant ce dernier WO2005083818A1 (fr)

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US10367218B2 (en) 2014-10-29 2019-07-30 Nissan Motor Co., Ltd. Electrode catalyst layer for fuel cell, method for producing the same, and membrane electrode assembly and fuel cell using the catalyst layer
US10535881B2 (en) 2013-04-25 2020-01-14 Nissan Motor Co., Ltd. Catalyst and electrode catalyst layer, membrane electrode assembly, and fuel cell using the catalyst
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JP2008517426A (ja) * 2004-12-17 2008-05-22 エルジー・ケム・リミテッド 燃料電池用電極触媒
WO2014175099A1 (fr) * 2013-04-25 2014-10-30 日産自動車株式会社 Catalyseur, couche de catalyseur d'électrode l'utilisant, ensemble membrane-électrode et pile à combustible
WO2014175105A1 (fr) * 2013-04-25 2014-10-30 日産自動車株式会社 Catalyseur, et couche de catalyseur d'électrode, ensemble d'électrode de film, et pile à combustible comprenant chacun ledit catalyseur
JPWO2014175099A1 (ja) * 2013-04-25 2017-02-23 日産自動車株式会社 触媒ならびに当該触媒を用いる電極触媒層、膜電極接合体および燃料電池
JPWO2014175105A1 (ja) * 2013-04-25 2017-02-23 日産自動車株式会社 触媒ならびに当該触媒を用いる電極触媒層、膜電極接合体および燃料電池
US9947934B2 (en) 2013-04-25 2018-04-17 Nissan Motor Co., Ltd. Catalyst and electrode catalyst layer, membrane electrode assembly, and fuel cell using the catalyst
US10535881B2 (en) 2013-04-25 2020-01-14 Nissan Motor Co., Ltd. Catalyst and electrode catalyst layer, membrane electrode assembly, and fuel cell using the catalyst
US10573901B2 (en) 2013-04-25 2020-02-25 Tanaka Kikinzoku Kogyo K.K. Catalyst and manufacturing method thereof, and electrode catalyst layer using the catalyst
US11031604B2 (en) 2013-04-25 2021-06-08 Nissan Motor Co., Ltd. Catalyst and electrode catalyst layer, membrane electrode assembly, and fuel cell using the catalyst
JP2015160178A (ja) * 2014-02-28 2015-09-07 東洋インキＳｃホールディングス株式会社 スルホン化炭素触媒及びその製造方法、及び該スルホン化炭素触媒を用いた触媒インキ並びに燃料電池
US10367218B2 (en) 2014-10-29 2019-07-30 Nissan Motor Co., Ltd. Electrode catalyst layer for fuel cell, method for producing the same, and membrane electrode assembly and fuel cell using the catalyst layer

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