WO2016068116A1 - Catalyseur d'électrode et son procédé de production - Google Patents

Catalyseur d'électrode et son procédé de production Download PDF

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WO2016068116A1
WO2016068116A1 PCT/JP2015/080202 JP2015080202W WO2016068116A1 WO 2016068116 A1 WO2016068116 A1 WO 2016068116A1 JP 2015080202 W JP2015080202 W JP 2015080202W WO 2016068116 A1 WO2016068116 A1 WO 2016068116A1
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platinum
tin
tin oxide
electrode catalyst
alloy
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PCT/JP2015/080202
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English (en)
Japanese (ja)
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三宅　行一
弘明 中原
彦睦 渡邉
直彦 阿部
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三井金属鉱業株式会社
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Priority to JP2016556575A priority Critical patent/JPWO2016068116A1/ja
Publication of WO2016068116A1 publication Critical patent/WO2016068116A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/88—Processes of manufacture
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an electrode catalyst for a fuel cell and a method for producing the same.
  • the polymer electrolyte fuel cell has a proton conductive polymer membrane such as a perfluoroalkylsulfonic acid type polymer as a solid electrolyte, and an oxygen electrode in which an electrode catalyst is applied to each surface of the solid polymer membrane.
  • a membrane electrode assembly having a fuel electrode is provided.
  • Electrocatalysts are generally formed by supporting various precious metal catalysts such as platinum on the surface of a conductive carbon material such as carbon black as a carrier.
  • a conductive carbon material such as carbon black
  • the electrode catalyst it is known that carbon is oxidized and corroded due to a potential change during operation of the fuel cell, and the supported metal catalyst is aggregated or dropped off. As a result, the performance of the fuel cell decreases as the operating time elapses. Therefore, in the manufacture of fuel cells, performance degradation is prevented by supporting a noble metal catalyst in a larger amount than is actually required on the carrier. However, this is not advantageous from an economic point of view.
  • load response durability is how much the initial characteristics are maintained when a load is repeatedly applied to the battery.
  • an object of the present invention is to provide an electrode catalyst for a fuel cell that can eliminate the various drawbacks of the above-described conventional technology.
  • the present invention comprises platinum supported on the surface of tin oxide particles,
  • the platinum is present in an alloyed state with tin, and provides an electrode catalyst in which the molar ratio of platinum to tin in the alloy is 1: 1.
  • the present invention provides a suitable method for producing the above electrode catalyst,
  • the fine particles of platinum are attached to the surface of the tin oxide particles,
  • FIG. 1 is an XRD chart of electrode catalysts obtained in Examples and Comparative Examples.
  • the electrode catalyst of the present invention has a support and a noble metal catalyst supported on the surface of the support.
  • the carrier is made of tin oxide.
  • the tin oxide used in the present invention is composed of an oxide of tin. It is known that tin oxide is a highly conductive substance. Examples of the tin oxide include SnO 2 which is a tetravalent tin oxide and SnO which is a divalent tin oxide. In particular, the tin oxide is preferably composed mainly of SnO 2 from the viewpoint of improving acid resistance. “Mainly composed of SnO 2 ” means that 50 mol% or more of tin contained in the oxide of tin is composed of SnO 2 .
  • Tin oxide is in the form of particles.
  • the particle size of the tin oxide particles is preferably 1 ⁇ m or more and 4 ⁇ m or less, and more preferably 1 ⁇ m or more and 3 ⁇ m or less.
  • the particle size refers to a volume cumulative particle diameter D 50 in the cumulative volume 50% by volume by laser diffraction scattering particle size distribution measuring method.
  • the primary particle constituting the tin oxide particle that is, the particle size of the object recognized as the smallest unit as the particle, judging from the apparent geometric form, can increase the specific surface area of the electrode catalyst support.
  • the thickness is preferably 5 nm or more and 100 nm or less, and more preferably 5 nm or more and 30 nm or less.
  • a shape which can enlarge a specific surface area For example, various shapes such as a spherical shape, a polyhedral shape, a plate shape, a spindle shape, or a mixture thereof can be adopted. A spherical shape is particularly preferable.
  • the primary particles of the tin oxide particles may be in an independent dispersed state. Or you may become the secondary particle which consists of an aggregate which the several primary particle aggregated. In the case of an aggregate, the particles may have an irregular shape in which irregularities are irregularly assembled. Or you may have the chain
  • the particle size of the tin oxide particles is measured by observing the electrode catalyst of the present invention with an electron microscope.
  • the ferret diameter of 100 or more particles is measured by electron microscope observation, and the average value is taken as the particle diameter.
  • the tin oxide may contain one or more elements selected from the group consisting of Ta, Nb, Sb, W, In, and V (hereinafter, this element is referred to as “additive element”). From the viewpoint of further improving the performance of the electrode catalyst.
  • the additive elements can be present inside the tin oxide particles or both inside and outside. When the additive element is present inside the tin oxide particles, the additive element is dissolved in the tin oxide or is present in the state of the additive element compound (for example, an oxide of the additive element) in the tin oxide. is doing.
  • the fact that the additive element is dissolved in the tin oxide means that the tin site in the tin oxide is replaced by the additive element. It is preferable that the additive element is dissolved in the tin oxide because the conductivity of the tin oxide containing the additive element as the carrier is increased.
  • the additive element When the additive element is present outside the tin oxide particle in addition to being present inside the tin oxide particle, the additive element is mainly present on the surface of the tin oxide particle in the state of the compound.
  • the additive element is present on the surface of the tin oxide particle in the form of its oxide.
  • the additive element is, for example, tantalum
  • examples of the tantalum oxide include Ta 2 O 5 , but are not limited thereto.
  • the content of the additive element contained in the tin oxide containing the additive element is represented by Ta (mol) / (Sn (mol) + Ta (mol)) ⁇ 100, taking the case where the additive element is Ta as an example. Preferably they are 1 mol% or more and 30 mol% or less. Hereinafter, this value is referred to as “additive element content”.
  • additive element content By setting the additive element content to 1 mol% or more, the conductivity of tin oxide containing the additive element can be sufficiently increased. Even if the additive element content exceeds 30 mol%, the conductivity as a carrier is not greatly improved.
  • the additive element content is more preferably 1 mol% or more and 15 mol% or less, more preferably 1 mol% or more and 10 mol% or less. is there.
  • the additive element content of the support composed of tin oxide containing the additive element can be measured, for example, by the following method.
  • the electrode catalyst is dissolved by an appropriate method to form a solution, this solution is analyzed by ICP emission analysis, and the concentration of tin and the concentration of additive elements are measured.
  • ICP emission analysis fluorescent X-ray (XRF) analysis can also be used.
  • one or more elements selected from the group consisting of Ta, Nb, Sb, In, W, and V are used.
  • Ta or Nb is preferably used from the viewpoint of a balance between performance and price.
  • a catalyst containing a noble metal is supported on the surface of the support.
  • a catalyst containing a noble metal an alloy in which platinum and tin are alloyed at a molar ratio of 1: 1 is used in the present invention.
  • an alloy in which platinum and tin are alloyed at a molar ratio of 1: 1 is supported on the above-described carrier to form an electrode catalyst, whereby a fuel cell having the electrode catalyst is obtained. It has been found that load response durability is improved.
  • Patent Document 1 described in the background section above when an alloy of platinum and tin is used instead of platinum alone, the output characteristics are inferior because of the catalyst. It is stated that this is due to a decrease in activity. However, this document does not give any consideration to the relationship between the alloying of platinum and the load response durability of the electrode catalyst.
  • the electrode catalyst of the present invention when this is measured by X-ray diffraction, an alloy in which platinum and tin are alloyed at a molar ratio of 1: 1 as a chemical species of platinum (hereinafter, this alloy is referred to as “PtSn”). It is preferable that a platinum-tin alloy such as PtSn 3 is not detected. Further, it is preferable that platinum alone is not detected. This further improves the load response durability of the electrode catalyst. “Not detected” means that a diffraction peak other than the diffraction peak derived from the PtSn alloy is not substantially observed in the X-ray diffraction measurement.
  • the PtSn alloy is advantageously supported on the surface of the carrier in the form of fine particles.
  • the particle diameter of the fine particles of the PtSn alloy is, for example, preferably 1 nm to 20 nm, and more preferably 1 nm to 8 nm.
  • the supported amount of Pt is more than 1% by mass and not more than 30% by mass with respect to the total mass of the electrode catalyst, that is, the mass of the carrier and the mass of the catalyst containing Pt. Preferably, it is more preferably 1% by mass or more and 20% by mass or less.
  • the amount of Pt supported can be determined by dissolving the electrode catalyst by an appropriate method to form a solution, and analyzing this solution by ICP emission analysis.
  • the PtSn alloy may cover the entire surface of the carrier evenly according to the amount of the PtSn alloy. For example, in the oxygen reduction reaction at the cathode of the fuel cell, if the reaction area of the PtSn alloy is too large for the oxygen diffusion amount Since the oxygen diffusion rate is limited, and the original catalytic activity may not be sufficiently exerted, it is better to discontinuously coat the carrier so that the surface of the carrier is exposed at an appropriate distance.
  • the electrode catalyst of the present invention in which a PtSn alloy is supported on a carrier preferably has a specific surface area of 10 m 2 / g or more and 130 m 2 / g or less, more preferably 20 m 2 / g or more and 130 m 2 / g or less.
  • the specific surface area is generally measured using physical adsorption such as nitrogen gas. For example, it can be measured by the BET method.
  • SA3100 manufactured by Bechman Coulter or flowsorb II manufactured by Micromeritics can be used for measurement of the specific surface area by the BET method.
  • an alloy of platinum and a transition metal may be supported on the carrier. This further improves the performance as an electrode catalyst.
  • the transition metal that forms an alloy with platinum include cobalt, nickel, titanium, molybdenum, manganese, iron, chromium, and palladium.
  • the same process may be performed in the presence of platinum and a transition metal salt in the presence of platinum.
  • This production method is roughly divided into (i) a carrier production step, (ii) a platinum loading step, and (iii) a platinum and tin alloying step.
  • a carrier production step a carrier production step
  • a platinum loading step a platinum loading step
  • a platinum and tin alloying step a platinum and tin alloying step
  • the carrier can be suitably produced by a known method such as a wet synthesis method or a plasma synthesis method.
  • a target carrier can be obtained by generating a tin precipitate from a solution containing a tin source and, if necessary, an additive element source, and then firing the precipitate.
  • an additive element source is also used, a co-precipitate containing tin and the additive element is generated, and then the co-precipitate is baked to obtain a target carrier.
  • the plasma synthesis method includes a step of synthesizing a powder for spray drying, granulating the powder by the spray drying method, and plasma synthesizing the obtained granulated body.
  • the carrier having the above-described chain structure site When used as the carrier, it can be suitably produced by a chemical flame method. Details of a method for producing a carrier having a chain structure site using the chemical flame method are described in, for example, WO2011 / 064471.
  • the carrier obtained by adopting any one of the above-described methods has platinum supported on its surface.
  • a known method such as an ethanol method or a colloid method can be employed.
  • dinitrodiamine platinum nitric acid solution is diluted with pure water to make an aqueous solution, to which carrier is added and mixed and dispersed, then ethanol is added and mixed, heated under reflux and held for several hours.
  • the reduction temperature is preferably about 95 ° C., and the reduction time is preferably 3 to 6 hours.
  • a carrier is dispersed in a liquid containing a colloid containing platinum, and the colloid is supported on the carrier. More specifically, a reducing agent is added to a liquid containing a colloidal precursor containing platinum to reduce the precursor to generate a colloid containing platinum. Then, the carrier is dispersed in a liquid containing a colloid containing platinum that is generated, and the colloid is supported on the carrier as fine particles containing platinum. Details of the ethanol method are described, for example, in JP-A-9-47659. The details of the colloid method are described in, for example, WO2009 / 060582 (same as Patent Document 1 described above).
  • heat treatment is then performed.
  • This heat treatment is performed for the purpose of activating platinum and alloying with tin.
  • the heat treatment is preferably performed in a reducing atmosphere.
  • the reducing atmosphere include hydrogen and carbon monoxide.
  • Hydrogen is preferable in that it is free from problems such as catalyst poisoning of platinum fine particles and is easily available.
  • hydrogen when used, it may be used at a concentration of 100%, or preferably 0.1 to 50% by volume, more preferably 1 to 10% by volume with an inert gas such as nitrogen, helium or argon. You may dilute and use.
  • the temperature of the heat treatment is preferably set to be higher than 300 ° C. and lower than or equal to 500 ° C., more preferably higher than 300 ° C. and lower than or equal to 400 ° C., from the viewpoint of successfully activating platinum and alloying with tin.
  • the heating temperature in this range is higher than a conventionally employed temperature, for example, the heating temperature described in Patent Document 1.
  • a PtSn alloy having a 1: 1 molar ratio of platinum to tin can be successfully obtained.
  • the heating holding time after reaching the set holding temperature is preferably 1 minute to 4 hours, preferably 10 minutes to 2 hours, provided that the heating temperature is within this range. preferable.
  • the rate of temperature rise is preferably 1 ° C./min or more and 20 ° C./min, preferably 3 ° C./min or more and 10 ° C./min or less when the temperature rise starts from room temperature.
  • the temperature lowering rate can also be within this range, but it is preferable to rapidly cool to room temperature.
  • the target electrode catalyst is obtained.
  • This electrode catalyst is used by being contained in at least one of an oxygen electrode and a fuel electrode in a membrane electrode assembly having an oxygen electrode disposed on one surface of a solid polymer electrolyte membrane and a fuel electrode disposed on the other surface. be able to.
  • the electrode catalyst can be preferably contained in both the oxygen electrode and the fuel electrode.
  • the oxygen electrode and the fuel electrode preferably include a catalyst layer containing the electrode catalyst of the present invention and a gas diffusion layer.
  • the electrode catalyst is preferably in contact with the solid polymer electrolyte membrane.
  • the gas diffusion layer functions as a supporting current collector having a current collecting function. Furthermore, it has a function of sufficiently supplying gas to the electrode catalyst.
  • the gas diffusion layer those similar to those conventionally used in this kind of technical field can be used.
  • carbon paper and carbon cloth which are porous materials can be used. Specifically, it can be formed by, for example, a carbon cloth woven with yarns having a predetermined ratio of carbon fibers whose surfaces are coated with polytetrafluoroethylene and carbon fibers that are not coated.
  • solid polymer electrolyte those similar to those conventionally used in this kind of technical field can be used.
  • a perfluorosulfonic acid polymer-based proton conductor film a hydrocarbon polymer compound doped with an inorganic acid such as phosphoric acid, or an organic / inorganic hybrid polymer partially substituted with a proton conductor functional group
  • proton conductors in which a polymer matrix is impregnated with a phosphoric acid solution or a sulfuric acid solution.
  • the membrane electrode assembly is made into a polymer electrolyte fuel cell by providing a separator on each surface.
  • a separator for example, a separator in which a plurality of protrusions (ribs) extending in one direction are formed at a predetermined interval on the surface facing the gas diffusion layer can be used. Between adjacent convex parts, it is a groove part with a rectangular cross section. The groove is used as a supply / discharge flow path for an oxidant gas such as fuel gas and air. The fuel gas and the oxidant gas are supplied from the fuel gas supply unit and the oxidant gas supply unit, respectively.
  • Each separator disposed on each surface of the membrane electrode assembly is preferably disposed so that the grooves formed therein are orthogonal to each other.
  • the above configuration constitutes the minimum unit of the fuel cell, and a fuel cell can be configured from a cell stack formed by arranging several tens to several hundreds of this configuration in parallel.
  • the electrode catalyst of the present invention is used as an electrode catalyst of a solid polymer electrolyte fuel cell.
  • the electrode catalyst of the present invention is not a solid polymer electrolyte fuel cell. It can be used as an electrode catalyst in various fuel cells such as alkaline fuel cells, phosphoric acid fuel cells, direct methanol fuel cells, and the like.
  • Example 1 Production of carrier Tantalum-containing tin oxide particles used as a carrier were produced by a wet synthesis method. 3.047 g of TaCl 5 was added to 50 mL of ethanol to obtain a tantalum-containing solution in which it was dissolved. Separately, 88.493 g of Na 2 SnO 3 .3H 2 O was dissolved in pure water to obtain 1000 mL of a tin-containing aqueous solution. After adding 1330 mL of 0.5 mol / L nitric acid aqueous solution to the tantalum-containing solution, 1000 mL of tin-containing aqueous solution was added to this solution. This addition produced a precipitate in the liquid.
  • the liquid was allowed to stand at 25 ° C. for 1 hour to age the precipitate, and then the precipitate was collected by filtration and further washed with repulp. Subsequently, it was dried at 120 ° C. for 15 hours to obtain a solid.
  • the solid was pulverized in a mortar and then fired at 800 ° C. for 5 hours in an air atmosphere. After firing, for the purpose of atomization, the powder was further pulverized for 16 hours by a ball mill, filtered through a 1 ⁇ m membrane filter, and dried to obtain target tantalum-containing tin oxide particles.
  • the specific surface area of the tantalum-containing tin oxide measured by the BET method was 25.4 m 2 / g.
  • the content of tantalum was 2.5 mol%.
  • Example 1 In the “(iii) alloying of platinum by heat treatment” step in Example 1, the temperature of the heat treatment in a hydrogen atmosphere was changed from 350 ° C. to 80 ° C. Otherwise, an electrode catalyst was obtained in the same manner as in Example 1. The result of XRD measurement for the obtained electrode catalyst is shown in FIG. As shown in the figure, a diffraction peak derived from platinum alone was observed. Therefore, it is considered that all platinum is present in the state of platinum alone.
  • Example 2 In the “(iii) alloying of platinum by heat treatment” step in Example 1, the temperature of the heat treatment in a hydrogen atmosphere was changed from 350 ° C. to 150 ° C. Otherwise, an electrode catalyst was obtained in the same manner as in Example 1. The result of XRD measurement for the obtained electrode catalyst is shown in FIG. As shown in the figure, a diffraction peak derived from platinum alone and a peak derived from the Pt 3 Sn alloy were observed, but a peak derived from the PtSn alloy was not observed.
  • Electrode catalysts obtained in the examples and comparative examples were evaluated according to the conditions proposed by the Fuel Cell Practical Use Promotion Council (FCCJ) for the purpose of evaluating the load response durability. Further, cyclic voltammetry (CV) measurement was performed for the purpose of measuring an electrochemical active surface area (ECSA) before and after the potential cycle test. Specifically, the operation was performed in the following order of “electrode preparation” and “load response durability evaluation”.
  • FCCJ Fuel Cell Practical Use Promotion Council
  • Electrode preparation A glassy carbon (GC) disk electrode having a diameter of 5 mm was polished successively with 1 ⁇ m, 0.3 ⁇ m, and 0.05 ⁇ m alumina paste, and then ultrasonically cleaned with pure water. 47.3 mg of each electrocatalyst was weighed, added to a mixed solvent of water 7.6 mL and IPA 2.4 mL, and subjected to ultrasonic dispersion treatment for 15 minutes, and then 40 ⁇ L of 5% Nafion (registered trademark) solution was added. A catalyst ink was prepared by performing ultrasonic dispersion treatment for a minute. 10 ⁇ L of this was dropped onto a GC disk and dried at 60 ° C. for 30 minutes or more. Thus, an electrode for measurement was produced.
  • GC glassy carbon
  • Load response durability evaluation Measurement was carried out using an electrochemical measurement system HZ-7000 manufactured by Hokuto Denko Corporation. After purging N 2 into a 0.1 mol / l HClO 4 aqueous solution for 1 hour or longer, using a silver-silver chloride electrode as a reference electrode, operating in a potential range of ⁇ 0.25 to 0.8 V and a sweep rate of 100 mV / s The electrode, which is a pole, was cleaned 300 times. Thereafter, CV measurement was performed under the same conditions, and ECSA before the potential cycle test was measured. The potential cycle test was carried out by repeating a rectangular wave holding 0.35V and 0.75V for 3 seconds each for a predetermined number of times.
  • the electrode catalyst obtained in the example that is, the electrode catalyst having a PtSn alloy was different from the electrode catalysts of Comparative Examples 1 and 2 having no PtSn alloy, and ECSA after 10,000 cycles. It can be seen that the load response durability is excellent.
  • an electrode catalyst having excellent load response durability is provided.

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Abstract

L'invention concerne un catalyseur d'électrode qui est formé par retenue de platine sur la surface de particules d'oxyde d'étain. Le platine présent est allié à l'étain, le rapport molaire entre le platine et l'étain dans l'alliage étant de 1 : 1. Les particules d'oxyde d'étain contiennent de façon optimale au moins un type d'élément additif choisi dans le groupe comprenant Ta, Nb, Sb, In, W et V. Le catalyseur d'électrode est, de façon optimale, produit par un procédé dans lequel de fines particules de platine sont déposées sur la surface de particules d'oxyde d'étain, et ensuite les particules d'oxyde d'étain sont soumises à un traitement thermique dans une atmosphère réductrice à une température supérieure à 300 °C mais inférieure ou égale à 500 °C afin de générer un alliage dans lequel le rapport molaire entre le platine et l'étain est de 1 : 1.
PCT/JP2015/080202 2014-10-29 2015-10-27 Catalyseur d'électrode et son procédé de production WO2016068116A1 (fr)

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JP5322110B2 (ja) * 2007-11-09 2013-10-23 国立大学法人九州大学 燃料電池用カソード電極材料の製造方法及び燃料電池用カソード電極材料並びに該カソード電極材料を用いた燃料電池
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JPH07246336A (ja) * 1994-01-24 1995-09-26 Tanaka Kikinzoku Kogyo Kk 燃料電池用アノード電極触媒及びその製造方法
JP2005149742A (ja) * 2003-11-11 2005-06-09 Nissan Motor Co Ltd 燃料電池用触媒坦持電極およびその製造方法
JP5322110B2 (ja) * 2007-11-09 2013-10-23 国立大学法人九州大学 燃料電池用カソード電極材料の製造方法及び燃料電池用カソード電極材料並びに該カソード電極材料を用いた燃料電池
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WO2015146454A1 (fr) * 2014-03-28 2015-10-01 国立大学法人山梨大学 Catalyseur d'électrode et procédé de production de catalyseur d'électrode

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Publication number Priority date Publication date Assignee Title
JP2017174561A (ja) * 2016-03-22 2017-09-28 日産自動車株式会社 電極触媒の製造方法

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