WO2015050046A1 - Catalyseur d'électrode et son procédé de production - Google Patents

Catalyseur d'électrode et son procédé de production Download PDF

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WO2015050046A1
WO2015050046A1 PCT/JP2014/075579 JP2014075579W WO2015050046A1 WO 2015050046 A1 WO2015050046 A1 WO 2015050046A1 JP 2014075579 W JP2014075579 W JP 2014075579W WO 2015050046 A1 WO2015050046 A1 WO 2015050046A1
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noble metal
carrier
electrode
electrode catalyst
tin
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PCT/JP2014/075579
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English (en)
Japanese (ja)
Inventor
雄一 妹尾
克良 柿沼
内田　誠
内田　裕之
渡辺　政廣
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三井金属鉱業株式会社
国立大学法人山梨大学
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Priority to JP2015540467A priority Critical patent/JP6471979B2/ja
Publication of WO2015050046A1 publication Critical patent/WO2015050046A1/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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M2008/1095—Fuel cells with polymeric 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

  • the present invention relates to an electrode catalyst suitably used 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.
  • Patent Document 1 tin oxide particles doped with various elements are used in an aggregated state, whereas in Patent Document 2, five or more tin oxide particles are fused to each other. Electrocatalysts having a chain-like or tuft-like structure structure have been proposed.
  • an object of the present invention is to provide an electrode catalyst whose performance is further improved as compared with the above-described prior art, and a method for easily producing such an electrode catalyst.
  • the conductivity of an electrode catalyst is improved by supporting a catalyst containing a noble metal on a carrier having a specific structure by a specific method. did. Furthermore, it has also been found that the conductivity of the electrode catalyst is further improved by alloying the noble metal with tin which is a constituent element of the support when the catalyst containing the noble metal is supported.
  • the present invention has been made based on the above knowledge, and a plurality of particles containing tin oxide and one or more additive elements selected from the group consisting of Nb, Sb, Ta, In and V are beaded.
  • An electrocatalyst comprising a support having a continuous chain structure portion and a catalyst containing a noble metal supported on the surface of the support, wherein at least a part of the noble metal forms an alloy with tin.
  • the present invention also provides a method for producing the electrode catalyst, wherein a reducing agent is added to a liquid containing a precursor of a colloid containing a noble metal, the precursor is reduced to produce a colloid containing a noble metal,
  • a support having a chain structure portion in which a plurality of particles containing tin oxide and one or more additive elements selected from the group consisting of Nb, Sb, Ta, In, and V are arranged in a bead shape includes a noble metal.
  • the present invention provides a method for producing an electrocatalyst comprising a step of heat-treating the carrier after drying supporting fine particles containing the noble metal in a reducing atmosphere.
  • an electrode catalyst with further improved conductivity is provided. Moreover, according to the present invention, such an electrode catalyst can be easily produced.
  • FIG. 1 is a schematic view showing a flame method apparatus used in the present invention.
  • FIG. 2 is a schematic diagram showing a partial view of a spray nozzle in the flame method apparatus shown in FIG.
  • FIG. 3 is a transmission electron microscope image of the electrode catalyst obtained in Example 2.
  • FIG. 4 is a graph showing the XPS measurement results of the electrode catalyst obtained in Example 1.
  • FIG. 5 is a diffraction diagram showing the XRD measurement results of the electrode catalysts obtained in Examples 1, 4 and 5.
  • FIG. 6 is a graph showing XPS measurement results of the electrode catalysts obtained in Examples 4 and 5.
  • FIG. 7 is a transmission electron microscope image of the carrier used in Example 6.
  • FIG. 8 is a transmission electron microscope image of the carrier used in Comparative Example 4.
  • FIG. 9 is a schematic diagram showing a method for measuring the conductivity of the electrode catalysts obtained in the examples and comparative examples.
  • the electrode catalyst of the present invention has a support and a catalyst containing a noble metal supported on the surface of the support.
  • the carrier is one in which tin oxide contains one or more elements selected from the group consisting of Nb, Sb, Ta, In, and V (hereinafter, these elements are referred to as “added elements”).
  • 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.
  • the tin oxide is preferably composed mainly of SnO 2 from the viewpoint of improving acid resistance.
  • “Mainly composed of SnO 2 ” means that the ratio of SnO 2 in the tin oxide is 50 mol% or more in terms of tin element.
  • ⁇ ⁇ Tin oxide containing additive elements is in the form of particles.
  • a plurality of these particles are aggregated to form a specific structure which will be described later, thereby forming an electrode catalyst carrier.
  • the particle size of the individual particles constituting this structure is preferably 5 nm or more and 100 nm or less, more preferably 5 nm or more and 30 nm or less, from the viewpoint that the specific surface area of the electrode catalyst support can be increased.
  • 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 particle size of the tin oxide particles containing the additive element 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 additive element can be present inside the tin oxide particles, or both inside and outside.
  • 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, niobium
  • examples of niobium oxide include Nb 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 Nb (mol) / (Sn (mol) + Nb (mol)) ⁇ 100, taking the case where the additive element is Nb as an example. It is 0.1 mol% or more and 40 mol% or less. Hereinafter, this value is referred to as “additive element content”.
  • additive element content By setting the additive element content to 0.1 mol% or more, the conductivity of tin oxide containing the additive element can be sufficiently increased. Even if the additive element content exceeds 8 mol%, the conductivity as a carrier is not greatly improved.
  • the conductivity as a carrier similarly maintains a high value up to about 40 mol% even if the additive element content exceeds 8 mol%.
  • the additive element content may be 0.5 mol% or more and 8 mol% or less, particularly 1 mol% or more and 4 mol% or less. More preferred.
  • 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 Nb, Sb, Ta, In, and V are used as the additive element.
  • Nb or Ta is preferably used from the viewpoint of a balance between performance and price.
  • the carrier which is an aggregate of tin oxide particles containing an additive element, has a chain structure portion in which a plurality of the particles are connected in a bead shape.
  • the particle is bonded to two or more other particles. “Coupled” means that two particles are fused and integrated, and the distance R C between the centers of gravity of each particle is smaller than the sum of the ferret diameters (R 1 , R 2 ) of the particles (R C ⁇ R 1 + R 2 )
  • each particle may be linear, or may be a wavy curve, random zigzag, or fractal. Furthermore, a single chain structure portion may be branched into two or more lines at any position of the chain structure portion.
  • the number of particles constituting the chain structure portion is 5 or more from the viewpoint of increasing the specific surface area of the support, reducing the contact resistance, and forming a conductive path.
  • the number is 50 or more, more preferably 5000 or more.
  • the upper limit of the number is not particularly limited, but if a large number of particles are connected to about 5000, a satisfactory increase in specific surface area can be obtained.
  • the carrier may be composed only of the chain structure portion of the tin oxide particles containing the additive element, or may be composed of both the chain structure portion and other form portions. Examples of other forms of sites include agglomerated sites of tin oxide particles containing an additive element. It is necessary that at least one chain structure site exists in the carrier. When two or more chain structure sites are present, the number of particles constituting each chain structure site may be the same or different.
  • a catalyst containing a noble metal is supported on the surface of the support.
  • the catalyst containing a noble metal is a catalyst forming a noble metal itself or an alloy containing a noble metal.
  • the alloy containing a noble metal one kind of noble metal described below can be used alone, or two or more kinds can be used in combination. Or the alloy which consists of said noble metal and other metals, Comprising:
  • the said noble metal is included 10 mass% or more.
  • Noble metals that can be suitably used in the present invention are not particularly limited as long as they have electrochemical catalytic activity for oxygen reduction (and hydrogen oxidation), and known materials can be used.
  • the noble metal is selected from Pt, Ru, Ir, Pd, Rh, Os, Au, Ag, and the like.
  • “Other metals” are not particularly limited, but Sn, Ti, Ni, Co, Fe, W, Ta, Nb, and Sb can be given as preferable examples. These can be used alone or in combination of two or more.
  • Pt and alloys containing Pt are electrochemical catalysts for oxygen reduction (and hydrogen oxidation) in the temperature range around 80 ° C., which is the operating temperature of a polymer electrolyte fuel cell. Since the activity is high, it can be particularly preferably used.
  • the catalyst containing the noble metal is advantageously supported on the surface of the carrier in the form of fine particles.
  • the particle diameter of the fine particles containing the noble metal is preferably set to 1 nm or more and 20 nm or less, for example.
  • the particle diameter of the fine particle containing the noble metal can be obtained by the average value of the crystallite diameter obtained from the half-value width of the diffraction peak of the catalyst containing the noble metal in X-ray diffraction or the particle diameter of the catalyst containing the noble metal examined from an electron microscope image. it can.
  • the supported amount of the catalyst containing the noble metal is preferably more than 0.2 mass% and 50 mass% or less with respect to the total mass of the electrode catalyst, that is, the total mass of the support and the mass of the catalyst containing the noble metal.
  • the content is more preferably 0% by mass or more and 18.0% by mass or less, and further preferably 3.0% by mass or more and 9.0% by mass or less.
  • the crystal system and presence / absence of this alloy (hereinafter also referred to as noble metal tin alloy) in the electrode catalyst can be confirmed by, for example, X-ray diffraction (XRD) or X-ray photoelectron spectroscopy (XPS).
  • XRD X-ray diffraction
  • XPS X-ray photoelectron spectroscopy
  • the crystal system of the noble metal tin alloy is hexagonal or cubic because conductivity is further improved.
  • the value of [A1 (mol) / A (mol)] ⁇ 100 (%), which is the ratio of the noble metal that is a noble metal tin alloy in the catalyst containing the noble metal, is preferably large, particularly 100%. preferable.
  • the lower limit is not particularly limited, but is preferably 1% or more, and particularly preferably 20% or more from the viewpoint of the effect of the noble metal tin alloy on improving the conductivity of the carrier.
  • A1 represents the number of moles of the noble metal that is a noble metal tin alloy, and A represents the number of moles of the entire noble metal.
  • the results of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) can be referred to.
  • XRD X-ray diffraction
  • XPS X-ray photoelectron spectroscopy
  • Non-Patent Document 1 According to J. Llorca, P. Ramirez de la Piscina, JLG Fierro, J. Sales, N, Homs, J. Mol. Catal., 118 (1997) 101-111.
  • Sn binding energy of PtSn / SiO 2 in the case of forming Sd 3d 5/2 can be attributed to three peaks, 486.8 eV: Sn oxide, 484.9 eV: Sn of Pt and Sn alloy, respectively. , 483.6 eV: Sn 0 .
  • the catalyst containing the noble metal may cover the entire surface of the support evenly according to the amount of the catalyst supported.However, if the reaction area of the catalyst containing the noble metal is too large for the oxygen diffusion amount in the oxygen reduction reaction, the oxygen diffusion rate is controlled. Therefore, the original catalytic activity may not be sufficiently exhibited. Therefore, it is preferable to discontinuously coat the support so that the surface of the support is exposed at an appropriate distance.
  • the electrode catalyst has a large specific surface area due to the special shape of the carrier constituting the electrode catalyst.
  • the specific surface area is preferably 20 m 2 / g or more and 130 m 2 / g or less, more preferably 30 m 2 / g or more and 100 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.
  • This production method is roughly divided into (i) a carrier production step and (ii) a catalyst loading step including a noble metal.
  • a carrier production step a carrier production step
  • a catalyst loading step including a noble metal a catalyst loading step including a noble metal.
  • a carrier can be preferably produced by a chemical flame method.
  • a raw material liquid containing a compound containing a tin compound and an additive element and an organic solvent capable of dissolving these compounds is used.
  • an organic tin compound is preferably used.
  • a tin salt of an organic acid such as tin octylate or dibutyltin bisacetylacetonate (“Narsem Tin” (trade name) manufactured by Nippon Chemical Industry Co., Ltd.) can be used.
  • a tin compound can be used individually by 1 type or in combination of 2 or more types.
  • an organic compound containing the additive element is preferably used.
  • the additive element is niobium
  • the organic niobium compound for example, a niobium salt of an organic acid such as niobium octylate can be used.
  • the compound containing an additional element can be used individually by 1 type or in combination of 2 or more types.
  • aromatics or alcohols such as terpene oil, mineral spirits, octylic acid, methanol, ethanol, an aqueous solution thereof, a mixture thereof, or the like is used. be able to. Of these, it is preferable to use turpentine oil in view of viscosity and heat of combustion.
  • the concentration of the tin compound in the raw material liquid is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 14% by mass or less in terms of tin.
  • the concentration of the compound containing the additive element in the raw material liquid is preferably 0.004% by mass to 3.4% by mass in terms of the additive element, and 0.012% by mass to 0.95% by mass. More preferably.
  • the ratio of the tin compound and the compound containing the additive element in the raw material solution is adjusted to match the ratio of tin and the additive element in the target carrier.
  • the raw material liquid obtained in this way is supplied into a chemical flame with a fuel gas such as propane, methane, acetylene, hydrogen or nitrous oxide and burned to have a target carrier, that is, a chain structure site.
  • a carrier is obtained.
  • the temperature of the chemical flame is preferably set to 600 ° C. or higher and 2000 ° C. or lower, more preferably set to 1200 ° C. or higher and 1600 ° C. or lower.
  • the carrier When the carrier is obtained as described above, it is subjected to the catalyst loading step (ii) containing the noble metal.
  • the support In the supporting step, the support is dispersed in a liquid containing a colloid containing a noble metal, and the colloid containing the noble metal is supported on the support as fine particles containing the noble metal, and then heat treatment is performed. More specifically, (ii-a) a reducing agent is added to a liquid containing a colloidal precursor containing a noble metal to reduce the precursor to produce a colloid containing the noble metal, and the produced noble metal is contained.
  • a carrier is dispersed in a liquid containing a colloid, the colloid containing the noble metal is supported on the carrier as fine particles containing the noble metal, and (ii-b) the liquid is separated from the carrier carrying the fine particles containing the noble metal. Then, the carrier is dried, and (ii-c) the dried carrier carrying fine particles containing a noble metal is heat-treated in a reducing atmosphere.
  • the conditions for preparing the liquid containing the noble metal-containing colloid used in (ii-a) are not particularly limited, and may be set appropriately according to the selected noble metal precursor and the reducing agent.
  • the noble metal precursor for example, when platinum is used as the noble metal, chloroplatinic acid can be used.
  • the form when the carrier is dispersed in the solution containing the colloid containing the noble metal may be in a powder state or in a state dispersed in a liquid medium such as water or ethanol. The latter is desirable because a uniform solution can be reliably formed.
  • Examples of the reducing agent used for the reduction of the colloidal precursor containing the noble metal include sodium bisulfite (NaHSO 3 ), sodium borohydride, sodium triethylborohydride, hydrogen peroxide, and hydrazine. These may be used singly or in combination of two or more. Of these reducing agents, it is particularly preferable to use sodium bisulfite. Furthermore, after performing reduction with a certain reducing agent, reduction may be performed again with another reducing agent. By performing multistage reduction treatment in the liquid phase as described above, fine particles containing a noble metal can be supported in a highly dispersed state on a carrier.
  • the pH of the liquid containing the colloidal precursor containing the noble metal can be, for example, 1 or more and 10 or less, and 4 to 6 is particularly preferable.
  • a colloid solution in which a colloid containing a noble metal is uniformly dispersed without aggregation can be prepared.
  • a preferable temperature range when reducing the colloidal precursor containing the noble metal is 20 ° C. or more and 100 ° C. or less, and particularly preferably 50 ° C. or more and 70 ° C. or less.
  • the reduction time is usually from 10 minutes to 2 hours, provided that the temperature range is within this range.
  • the precursor of the colloid containing the noble metal is not particularly limited, and a liquid medium that is suitably used as a solvent, for example, water or one that is soluble in lower alcohols such as methanol and ethanol is selected. Specific examples include halides, nitrates, sulfates, oxalates and acetates of noble metal elements.
  • the liquid is separated from a carrier carrying fine particles containing a noble metal, and the carrier is dried.
  • the method for separating the liquid is not particularly limited, and usually a method is selected in which most of the liquid is removed by filtration, centrifugation, etc., and then the remaining liquid is evaporated and dried.
  • a drying method any of heat drying, reduced pressure drying, and natural drying may be used.
  • the atmosphere in which drying is performed is not particularly limited, and the atmospheric conditions such as an oxidizing atmosphere containing oxygen or an air atmosphere, an inert atmosphere containing nitrogen or argon, or a reducing atmosphere containing hydrogen are arbitrarily selected. You can choose. Usually, it is performed in an air atmosphere.
  • the temperature at which drying is performed is not particularly limited, and is preferably performed at a temperature of less than 150 ° C. from the viewpoint of preventing oxidation of the catalyst containing the noble metal.
  • an operation for removing impurities contained in the carrier may be performed.
  • chloroplatinic acid is used as the noble metal precursor
  • chloride ions may remain in the carrier.
  • the carrier is diluted with ultrapure water to form a slurry. It is preferable to prepare and boil the slurry. The boiling can be performed under atmospheric pressure. In order to ensure the removal of impurities, the dilution and boiling operations with ultrapure water may be repeated a plurality of times.
  • (Ii-c) is a step of activating fine particles containing a noble metal supported on a carrier.
  • the fine particles containing a noble metal dried through (ii-b) contain a lot of non-stoichiometric noble metal oxides, and therefore may have low catalytic activity. Therefore, in this step, the electrochemical catalytic action of the noble metal is activated by heat treatment in a reducing atmosphere. Further, the heat treatment generates an alloy of the noble metal element and tin contained in the support.
  • the temperature of the heat treatment is preferably set to 150 ° C. or more and 500 ° C. or less, more preferably 250 ° C. or more and 300 ° C. or less, from the viewpoint of successful activation of the noble metal and alloying with tin.
  • the heating temperature in the latter range is higher than a conventionally employed temperature, for example, the heating temperature described in Patent Document 1.
  • a high temperature setting it becomes possible to further promote alloying of noble metal and tin.
  • the heating temperature is excessively high, aggregation of the formed alloy particles proceeds, and the electrochemically active surface area in the oxygen reduction reaction may decrease. Therefore, it is preferable to perform the heat treatment at a temperature within the above range.
  • 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.
  • Examples of reducing atmospheres include hydrogen and carbon monoxide.
  • Hydrogen is preferable in that it is free from problems such as catalyst poisoning of fine particles containing noble metals and is easily available.
  • When hydrogen is 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 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 (I) Production of carrier The flame method synthesizer shown in FIGS. 1 and 2 was used. This apparatus is the same as that described in FIGS. 2 and 3 of Patent Document 2 (US2012 / 0295184A1). Niobium was used as an additive element. Carrier oxygen for transferring the raw material into the flame, oxygen for forming the flame and propane gas at a flow rate of 9 L / min, 5 L / min and 1 L / min, respectively, as shown in FIG. The gas was introduced from the gas inlets 31 and 32 and mixed in the gas mixer 33. The mixed gas was introduced into the stainless steel tube 34 and a chemical flame was generated by the burner 40.
  • a solution is prepared by dissolving tin octylate and niobium octylate in terpene oil at a molar ratio of tin and niobium of 0.99: 0.01, and this solution is supplied to the solution introduction unit 35 of the flame method synthesizer. Introduced in an amount of 1 to 10 g per minute, and passed through the mixer 37 and the stainless steel tube 38 by the oxygen gas contained in the carrier gas introduction part 36. The concentrations of tin octylate and niobium octylate in the solution were 13.6% and 0.11%, respectively, in terms of tin and niobium.
  • This solution was made into a mist through a fluid nozzle, an air nozzle, and a retainer cap 39 and introduced into the chemical flame by the burner 40.
  • the temperature of the chemical flame was raised to about 1400 ° C. by the combustion heat of propane gas and terpene oil, and a support made of niobium-containing tin oxide was obtained in the chemical flame.
  • the powder produced in FIG. 2 was recovered by the recovery filter 27.
  • the environment during powder synthesis can often be in a non-equilibrium state, so that the obtained powder may change over time.
  • carrier obtained by said procedure was heat-processed using the rotary kiln (made by Alpha Giken) for the purpose of stabilization by the heat processing in an equilibrium state.
  • niobium-containing tin oxide 5 g was inserted into a Tamman tube having a diameter of 5 cm, and the core tube was rotated at a rotation speed of 6 rpm.
  • the temperature was raised at 5 ° C./min and held at 800 ° C. for 4 hours. Thereafter, the temperature was lowered to about room temperature at 5 ° C./min, and the powder was recovered.
  • this support was observed with a transmission electron microscope, it was confirmed that five or more particles had a chain structure portion connected in a bead shape.
  • the average particle size of the particles was 20 nm.
  • the colloidal solution was fractionated so that the theoretical concentration of platinum when it was supported on 4 g of carrier was 5 mass% (the amount of platinum contained in the solution was 0.21 g). Then 4 g of carrier was added and mixed at 90 ° C. for 3 hours. Thereafter, the liquid was cooled and further solid-liquid separated. In order to remove chloride ions from the water-containing powder obtained by solid-liquid separation, it was diluted again with 1500 mL of distilled water and boiled at 90 ° C. for 1 hour, and the liquid was cooled and solid-liquid separated. This washing operation was performed four times. Finally, after solid-liquid separation, it was dried at 60 ° C. for 12 hours in the atmosphere.
  • the ratio of the peak area having the apex in the range of less than 486.0 eV and 484.9 eV or more to the total Sn3d 5/2 spectral peak area is referred to as an alloying ratio 1.
  • alloying ratio of 2 the area ratio of the alloy per contact area of platinum and the support was converted in consideration of the area coverage of the support by platinum.
  • the ratio was 22.3%.
  • the BET specific surface area of the electrode catalyst carrier was 25 m 2 / g.
  • the contact area was calculated as follows.
  • the amount (g) of platinum present per 1 g of the carrier was calculated from the platinum loading analyzed by ICP, and converted to volume using the density of platinum. Thereafter, the number of platinum particles per 1 g of the carrier was calculated in terms of true spheres using the particle diameter of platinum.
  • the contact area between platinum and the carrier was the number of platinum particles ⁇ 2 ⁇ the hemispherical cross-sectional area of platinum particles (see FIG. 3 described later).
  • the platinum particle diameter was calculated by observing about 100 platinum particles with a transmission electron microscope (TEM). As a result of observation, the supported platinum and its alloy particles were often hemispherically bonded to the support, and therefore a factor of x2 was adopted (see FIG. 3 described later).
  • TEM transmission electron microscope
  • Example 1 [Examples 2 and 3 and Comparative Example 1]
  • the theoretical concentration of platinum when supported on 4 g of carrier is the desired concentration (10% (Example 2), 20% (Example 3), 0.5% (Comparative Example 1). )
  • An electrode catalyst was obtained in the same manner as in Example 1 except that the amount of the colloidal solution was adjusted.
  • Table 1 shows the amount of platinum supported in the electrode catalysts in Examples 2 and 3 and Comparative Example 1, and the proportion of platinum alloyed with tin (alloying proportions 1 and 2).
  • FIG. 3 shows a TEM image of the electrode catalyst obtained in Example 2. As is clear from the figure, most of the catalysts containing noble metals are attached to the support in a hemispherical shape.
  • Example 4 In Example 3 (ii), except that the temperature of the heat treatment for activation of platinum and alloying of platinum and tin was set to 250 ° C. (Example 4) and 300 ° C. (Example 5). In the same manner as in Example 3, an electrode catalyst was obtained. In Example 4, the amount of platinum supported on the electrode catalyst was 13.3% by mass.
  • the result of XPS measurement is shown in FIG. As is clear from the figure, a 3d 5/2 peak of Sn was confirmed in the vicinity of 485.9 eV, and it was confirmed that an alloy was formed. On the other hand, the result of the XRD measurement is shown in FIG.
  • the alloy was PtSn and its crystal system was hexagonal. Of platinum, the alloying ratio 1 alloyed with tin was 4.4%. The alloying ratio 2 was 31.0%. The BET specific surface area of the electrode catalyst carrier was 25 m 2 / g.
  • Example 6 An electrode catalyst was obtained in the same manner as in Example 1 except that the niobium content in the support was 4% in Example 1 (i). A transmission electron microscope image of this carrier is shown in FIG. As is apparent from the figure, this carrier has a chain structure portion in which a plurality of particles are linked in a beaded manner.
  • Example 7 In Example 4, the heat treatment for activation of platinum and alloying of platinum and tin was performed for 2 hours in a hydrogen atmosphere with a concentration of 100%. Except this, it carried out similarly to Example 4, and obtained the electrode catalyst. Evaluation similar to Example 4 was performed about the obtained electrode catalyst. The results are shown in Table 1.
  • Example 2 This comparative example is an example using a carrier not containing niobium.
  • niobium octylate was not used during the production of the carrier. Except for this, an electrode catalyst was obtained in the same manner as in Example 1.
  • Example 3 In this comparative example, platinum is not supported on the carrier. In Example 6, the step (ii) was not performed. Except this, the procedure was the same as in Example 6.
  • This comparative example is an example in which a carrier having no chain structure portion in which particles are arranged in a bead shape is used.
  • 88.493 g of sodium stannate trihydrate was weighed, and pure water was added thereto to make 1064 g, followed by stirring and dissolution to obtain a sodium stannate solution.
  • 3.6322 g of niobium chloride (NbCl 5 ) was weighed and dissolved in 83 ml of absolute ethanol, and 902 g of a 12 g / L nitric acid solution was added thereto to obtain a niobium chloride nitric acid solution.
  • the niobium chloride nitric acid solution was added to the sodium stannate solution and stirred for 1 hour. Filtration and pure water washing were performed until the electrical conductivity of the supernatant liquid during filtration was 45 mS / cm or less.
  • the obtained cake was dried at 120 ° C. overnight and crushed with a mortar. After the pulverized product was calcined at 800 ° C. for 5 hours in the atmosphere, 25 g of the calcined powder was mixed with 100 g of pure water to form a slurry, and this slurry was pulverized with a ball mill for 16 hours. Thereafter, the slurry was filtered, the filter cake was dried at 120 ° C.
  • this carrier does not have a chain structure portion in which a plurality of particles are linked in a bead shape.
  • Comparative Example 6 This comparative example is an example in which platinum was not supported on a carrier in a Nb 1 mol% system. Specifically, in Example 1, the step (ii) was not performed. Except for this, an electrode catalyst was obtained in the same manner as in Example 1.
  • This comparative example is an example where no noble metal was reduced in Example 4. Specifically, the step (ii-c) was not performed in Example 4. Except this, it carried out similarly to Example 4, and obtained the electrode catalyst.
  • the sample thickness under a constant pressure is adjusted by changing the filling amount such as 0.5 g, 1.5 g, and 2.0 g
  • the sample thickness is plotted on the x-axis and the resistance is plotted on the y-axis.
  • the y-intercept with a thickness of 0 was calculated as the contact resistance in the two-terminal method, and the resistance of the sample was calculated by subtracting from the measured value.
  • the resistivity was calculated from the dimensions of the green compact, and the reciprocal thereof was used to calculate the conductivity.
  • Table 1 The measurement results are shown in Table 1 below. The same measurement was performed on the carrier before carrying platinum, and the change in conductivity before and after carrying platinum (conductivity after carrying / conductivity before carrying) was determined. The results are also shown in Table 1.
  • the crystal system of the alloy is either cubic or hexagonal, but the conductivity is improved, but the hexagonal crystal has a higher conductivity improvement rate.
  • Comparative Example 2 the higher the niobium content, the better the improvement rate of the conductivity after reduction.
  • the improvement in conductivity after platinum loading and reduction is about twice, which is much smaller than in Examples 1 and 6. This is considered to indicate that the presence of the dopant Nb is extremely important, and it is important that the conductivity of the carrier is improved to some extent by the presence of the dopant.
  • the conductivity enhancement effect by the dopant is observed from a niobium concentration of about 0.1 mol%, so the lowest niobium concentration in this example Is 1 mol%, but it is estimated that the effect of improving conductivity is exhibited from about 0.1 mol%. Further, the present inventor shows that even when doping niobium until its concentration reaches about 8 mol%, the conductivity of the carrier, which is not related to Pt loading or reduction, does not change significantly compared to the niobium concentration of 4 mol%. Have confirmed.
  • Electrode catalysts obtained in Examples 3 and 5 were subjected to cyclic voltammetry (CV) and convective voltammetry (LSV) using a rotating disk electrode. Specifically, operations were performed in the following order of “electrode preparation”, “CV measurement”, and “ORR activity evaluation”.
  • the glassy carbon (GC) disk electrode of the electrode fabricated diameter 5 mm 1 [mu] m, 0.3 [mu] m, and sequentially polished using 0.05 ⁇ m alumina paste was then ultrasonically washed with pure water.
  • a sample carrying platinum and subjected to the reduction heat treatment described in (ii-c) was subjected to 90 vol.
  • the mixture was dispersed with an ultrasonic homogenizer. This was dropped onto a GC disk and dried at room temperature for 12 hours or more. After drying, a 5% Nafion (registered trademark) solution was dropped onto the catalyst on the GC disk so as to have a film thickness of 50 nm, and dried at room temperature for 12 hours or more.
  • CV measurement was performed using an electrochemical measurement system HZ-5000 manufactured by Hokuto Denko Corporation. After purging N 2 in a 0.1 M HClO 4 aqueous solution for 1 hour or longer, using a reversible hydrogen electrode (RHE) as a reference electrode, cleaning was performed 60 times at a potential range of 0.05 to 1.15 V and a sweep rate of 0.5 V / s. Carried out. Thereafter, the electrolyte was replaced with a new electrolyte solution, and CV measurement was carried out in the potential range of 0.05 to 1.0 V to make this measurement. The analysis of the electrochemical active surface area (ECSA) was carried out using an adsorption wave of hydrogen found at 0.4 V or less.
  • RHE reversible hydrogen electrode
  • Example 5 the activity-dominated current density j k (mA / cm 2 ) and mass specific activity (A / g ⁇ Pt ) of Example 5 were equivalent to those of Example 3.
  • the conductivity of the electrode catalyst is improved by the progress of alloying.
  • Example 8 (I) Production of carrier
  • a carrier in which tantalum was contained as an additive element in tin oxide was produced.
  • dibutyltin bisacetylacetonate (“Narsemtin” (trade name) manufactured by Nippon Chemical Industry Co., Ltd.) was used instead of tin octylate, and octyl was substituted for niobium octylate. Tantalum acid was used.
  • Dibutyltin bisacetylacetonate and tantalum octylate were blended so that the molar ratio of tin to tantalum was 0.975: 0.025, and dissolved in terpene oil to prepare a solution.
  • the concentrations of dibutyltin bisacetylacetonate and tantalum octylate in the solution were 13.6% and 0.53%, respectively, in terms of tin and tantalum.
  • a carrier was obtained in the same manner as in Example 1 except for this. When this support was observed with a transmission electron microscope, it was confirmed that five or more particles had a chain structure portion connected in a bead shape. The average particle size of the particles was 20 nm.
  • Example 9 In Example 8 (ii), the amount of colloidal solution was adjusted so that the theoretical concentration of platinum when supported on 4 g of the carrier was the desired concentration (10% (Example 9), 20% (Example 10)). An electrode catalyst was obtained in the same manner as in Example 1 except for the adjustment. The obtained electrode catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Comparative Example 8 This comparative example is an example in which platinum was not supported on the support made of tin oxide containing tantalum in Example 8. That is, in Example 8, the step (ii) was not performed. The rest was the same as in Example 8.

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Abstract

L'invention concerne un catalyseur d'électrode qui comprend : un support comportant un site de structure en chaîne où une pluralité de particules contenant au moins un type d'élément supplémentaire sélectionné dans un groupe comprenant le niobium (Nb), l'antimoine (Sb), le tantale (Ta), l'indium (In) et le vanadium (V) sont reliées sphériquement à un oxyde d'étain ; et un catalyseur comprenant un métal rare supporté sur la surface du support. Au moins une partie du métal rare forme un alliage avec l'étain. Idéalement, le catalyseur comprenant le métal rare disperse le support dans un liquide contenant un colloïde comportant le métal rare, réduit le colloïde comportant le métal rare et supporte ce colloïde sur le support sous forme de microparticules comportant le métal rare.
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WO2016068116A1 (fr) * 2014-10-29 2016-05-06 三井金属鉱業株式会社 Catalyseur d'électrode et son procédé de production
EP2966715A4 (fr) * 2013-03-06 2016-10-26 Mitsui Mining & Smelting Co Oxyde d'étain contenant du tantale pour matériau d'électrode de pile à combustible
JP2017157353A (ja) * 2016-02-29 2017-09-07 国立大学法人山梨大学 合金電極触媒およびにそれを用いた燃料電池
DE102017106833A1 (de) 2016-04-04 2017-10-05 Toyota Jidosha Kabushiki Kaisha Verfahren zur Herstellung einer Brennstoffzellenkatalysatorschicht
CN112714671A (zh) * 2018-10-19 2021-04-27 日本化学产业株式会社 负载型金属催化剂及其制造方法
WO2022045004A1 (fr) 2020-08-25 2022-03-03 国立大学法人山梨大学 Catalyseur métallique supporté
JPWO2022131293A1 (fr) * 2020-12-16 2022-06-23
WO2022145349A1 (fr) 2021-01-04 2022-07-07 国立大学法人山梨大学 Catalyseur métallique supporté

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WO2011065471A1 (fr) * 2009-11-27 2011-06-03 国立大学法人山梨大学 Porteur de charge à haut potentiel stable à base d'oxyde destiné à une pile à combustible polymère solide

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JP2007157711A (ja) * 2005-11-30 2007-06-21 Samsung Sdi Co Ltd 燃料電池用カソード触媒、燃料電池用膜電極接合体及び燃料電池システム
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Publication number Priority date Publication date Assignee Title
EP2966715A4 (fr) * 2013-03-06 2016-10-26 Mitsui Mining & Smelting Co Oxyde d'étain contenant du tantale pour matériau d'électrode de pile à combustible
JPWO2016068116A1 (ja) * 2014-10-29 2017-08-10 三井金属鉱業株式会社 電極触媒及びその製造方法
WO2016068116A1 (fr) * 2014-10-29 2016-05-06 三井金属鉱業株式会社 Catalyseur d'électrode et son procédé de production
JP2017157353A (ja) * 2016-02-29 2017-09-07 国立大学法人山梨大学 合金電極触媒およびにそれを用いた燃料電池
DE102017106833A1 (de) 2016-04-04 2017-10-05 Toyota Jidosha Kabushiki Kaisha Verfahren zur Herstellung einer Brennstoffzellenkatalysatorschicht
CN112714671B (zh) * 2018-10-19 2023-08-15 日本化学产业株式会社 负载型金属催化剂及其制造方法
CN112714671A (zh) * 2018-10-19 2021-04-27 日本化学产业株式会社 负载型金属催化剂及其制造方法
US11752490B2 (en) 2018-10-19 2023-09-12 Nihon Kagaku Sangyo, Co, Ltd. Supported metal catalyst and method for producing same
WO2022045004A1 (fr) 2020-08-25 2022-03-03 国立大学法人山梨大学 Catalyseur métallique supporté
JP7261417B2 (ja) 2020-12-16 2023-04-20 日本化学産業株式会社 酸化スズ結晶子連珠または酸化スズと酸化チタンの複合酸化物結晶子連珠
WO2022131293A1 (fr) * 2020-12-16 2022-06-23 日本化学産業株式会社 Cordon de perles de cristallite d'oxyde d'étain ou cordon de perles de cristallite d'un oxyde complexe d'oxyde d'étain et d'oxyde de titane
JPWO2022131293A1 (fr) * 2020-12-16 2022-06-23
WO2022145349A1 (fr) 2021-01-04 2022-07-07 国立大学法人山梨大学 Catalyseur métallique supporté

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