WO2015037721A1 - Particules composites conductrices, composition pour couche de catalyseur d'électrode pour pile à combustible, couche de catalyseur d'électrode pour pile à combustible, et pile à combustible - Google Patents

Particules composites conductrices, composition pour couche de catalyseur d'électrode pour pile à combustible, couche de catalyseur d'électrode pour pile à combustible, et pile à combustible Download PDF

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WO2015037721A1
WO2015037721A1 PCT/JP2014/074292 JP2014074292W WO2015037721A1 WO 2015037721 A1 WO2015037721 A1 WO 2015037721A1 JP 2014074292 W JP2014074292 W JP 2014074292W WO 2015037721 A1 WO2015037721 A1 WO 2015037721A1
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titanium oxide
particles
tin oxide
conductive composite
composite particles
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PCT/JP2014/074292
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English (en)
Japanese (ja)
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岳洋 米澤
山崎　和彦
真也 白石
洋利 梅田
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三菱マテリアル株式会社
三菱マテリアル電子化成株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • 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
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • 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
    • 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
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/086—Phosphoric acid fuel cells [PAFC]
    • 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
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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 conductive composite particles in which tin oxide (SnO 2 ) fine particles are formed on the surface of titanium oxide (TiO 2 ) particles.
  • the conductive composite particles have a large specific surface area and are suitable as a support for platinum nanoparticle catalysts of fuel cell electrodes.
  • the present invention also relates to a composition for a fuel cell electrode catalyst layer, a fuel cell electrode catalyst layer, and a fuel cell.
  • FIG. 1 shows an example of a schematic diagram of a cross-sectional structure of a fuel cell.
  • the fuel cell 1 includes an electrolyte membrane 20 sandwiched between a fuel electrode 10 and an air electrode 30, and includes a fuel electrode catalyst layer 11 of the fuel electrode 10 and an air electrode catalyst layer 31 of the air electrode 30.
  • a carbon material on which platinum nanoparticles are supported is usually used.
  • the catalyst carrier used in the air electrode catalyst layer 11 of the fuel electrode 10 must have high resistance to oxidation and strong acid, and a carbon material is insufficient.
  • tin oxide is suitable as a catalyst carrier for the air electrode catalyst layer 31 because of its high resistance to oxidation and strong acid.
  • the present inventors examined the use of tin oxide fine particles having a large specific surface area as a support for the platinum nanoparticle catalyst, but the aggregation was severe and the handling property was poor.
  • a tin oxide film was formed on the surface of titanium oxide particles having high resistance to oxidation and strong acid based on a known technique (Patent Document 1), but it is a smooth film shape in which tin oxide is integrally linked. The specific surface area of the tin oxide film is small. For this reason, platinum nanoparticle catalysts supported on the tin oxide film were aggregated.
  • a tin oxide fine particle layer having a large specific surface area was formed on the surface of the titanium oxide particles by the conventional technique, the tin oxide fine particles were separated from the titanium oxide particles.
  • An object of the present invention is to provide highly conductive conductive composite particles in which a tin oxide fine particle layer having high adhesion and a large specific surface area is formed on the surface of a titanium oxide powder.
  • the present inventors have intensively studied and the reason why the tin oxide fine particle layer formed by the conventional technique peels from the titanium oxide particles is that the lattice image of the tin oxide fine particles and the lattice image of the titanium oxide particle surface are not parallel. I found out. Then, by making the length of the lattice image of tin oxide parallel to the lattice image of titanium oxide 80% or more with respect to the length of the lattice image of titanium oxide parallel to the surface of the titanium oxide particles, tin oxide It has been found that separation of fine particles from titanium oxide particles can be suppressed.
  • the present invention relates to conductive composite particles, a composition for an electrode catalyst layer of a fuel cell, an electrode catalyst layer of a fuel cell, and a fuel cell that have solved the above problems by any one of the following aspects.
  • Conductive composite particles in which the surface of titanium oxide particles is coated with a porous tin oxide fine particle layer In the high-resolution transmission electron microscope image, the length of the lattice image of tin oxide parallel to the lattice image of the titanium oxide is 80 with respect to the length of the lattice image of titanium oxide parallel to the surface of the titanium oxide particles. %. Conductive composite particles characterized by being at least%.
  • the titanium oxide includes a rutile crystal structure
  • the tin oxide includes a rutile crystal structure
  • the (110) plane of the rutile type crystal structure of the titanium oxide and the (110) plane of the rutile type crystal structure of the tin oxide are parallel to each other in the electron diffraction pattern.
  • a composition for an electrode catalyst layer of a fuel cell comprising the conductive composite particles according to [1] or [2] above and a dispersion medium.
  • An electrode catalyst layer for a fuel cell containing the conductive composite particles according to [1] or [2].
  • a fuel cell comprising the electrode catalyst layer of the fuel cell according to [4].
  • the lattice image of titanium oxide parallel to the surface of the titanium oxide particles refers to the titanium oxide particles in the high-resolution transmission electron microscope image. 4th to 8th layers from the center of the interface of the tin oxide fine particles in the region of width: 50 nm and thickness: 5 nm parallel to the interface, from the surface of the titanium oxide particles and the interface between the titanium oxide particles and the tin oxide fine particles It is a lattice image in which the absolute value of the angle formed by the lattice image of titanium oxide is within 10 °.
  • the lattice image of tin oxide parallel to the lattice image of titanium oxide means a width parallel to the interface from the center of the interface between the titanium oxide particles and the tin oxide particles in the high-resolution transmission electron microscope image. : Within a region of 50 nm and thickness: 5 nm, a lattice image of titanium oxide in the fourth to eighth layers from the interface between the titanium oxide particles and the tin oxide fine particles parallel to the surface of the titanium oxide particles, and the titanium oxide particles And the tin image of the fourth to eighth layers from the interface between the tin oxide fine particles and the tin oxide fine particles are lattice images having an absolute value of 10 ° or less.
  • the length of the lattice image of tin oxide parallel to the lattice image of the titanium oxide relative to the length of the lattice image of titanium oxide parallel to the surface of the titanium oxide particles means the following. That is, in the high-resolution transmission electron microscope image, the titanium oxide particles and the tin oxide fine particles are within the region of the width: 50 nm and the thickness: 5 nm parallel to the interface from the center of the interface between the titanium oxide particles and the tin oxide fine particles.
  • the length (Lt) of the lattice image of titanium oxide having an absolute value of an angle of 10 ° or less with respect to the surface of the titanium oxide particles is measured with respect to the lattice images of the fourth to eighth layers of titanium oxide from the interface.
  • the absolute value of the angle with respect to the lattice image of titanium oxide is 10 ° or less with respect to the lattice image of the fourth to eighth layers from the interface between the titanium oxide particles and the tin oxide fine particles.
  • the length (Ls) of the lattice image of tin oxide is measured.
  • the Ls and Lt for each layer are used [[Ls / Lt ) ⁇ 100].
  • the average of [(Ls / Lt) ⁇ 100] for each calculated layer is obtained, which means that this average is 80% or more.
  • the (110) plane of the rutile crystal structure of the titanium oxide and the (110) plane of the rutile crystal structure of the tin oxide are parallel in the electron diffraction pattern. “Yes” means the following. That is, an electron diffraction pattern with both the titanium oxide and the tin oxide of the conductive composite particles in view is obtained using a transmission electron microscope. In this electron beam diffraction pattern, starting from the direct spot and passing through the [110] diffraction point, straight lines passing through the first and second diffraction points are drawn from the direct spot in the [110] direction. . This straight line is taken as a reference line in the [110] direction.
  • the [110] direction of the rutile crystal structure of titanium oxide and the [110] direction of the rutile crystal structure of tin oxide are: It is parallel on the electron diffraction pattern, and the (110) plane of the rutile crystal structure of titanium oxide and the (110) plane of the rutile crystal structure of tin oxide are parallel on the electron diffraction pattern. Is equivalent.
  • the lattice image of titanium oxide is longer than the length of the lattice image of titanium oxide parallel to the titanium oxide particle surface. Since the length of the parallel lattice image of tin oxide is 80% or more, the adhesion between the tin oxide fine particle layer and the titanium oxide particles is high. Further, since the porous tin oxide fine particle layer is formed on the titanium oxide particles, the conductive composite particles of [1] have a large specific surface area and high conductivity.
  • carrier of a platinum nanoparticle catalyst. can be provided.
  • the conductive composite particles of [1] or [2] contained in the electrode catalyst layer of the fuel cell have high adhesion between the tin oxide fine particle layer and the titanium oxide particles, Since the surface area is large and the conductivity is high, a highly reliable electrode catalyst layer for a fuel cell can be provided. According to said [5], it is possible to provide a highly reliable fuel cell provided with the electrode catalyst layer of the fuel cell of said [4].
  • FIG. 2 is a scanning electron micrograph of conductive composite particles produced in Example 1.
  • FIG. 2 is a transmission electron micrograph of conductive composite particles produced in Example 1.
  • FIG. 2 It is Ti mapping by the energy dispersive X-ray-spectral-analysis apparatus attached to the transmission electron microscope of the electroconductive composite particle produced in Example 1.
  • FIG. 2 It is Sn mapping by the energy dispersive X-ray-spectral-analysis apparatus attached to the transmission electron microscope of the electroconductive composite particle produced in Example 1.
  • FIG. 2 is a transmission electron micrograph of conductive composite particles produced in Example 1.
  • FIG. 2 is a high-resolution transmission electron microscope image of conductive composite particles produced in Example 1.
  • FIG. 3 is a high-resolution transmission electron microscope image of conductive composite particles produced in Comparative Example 1.
  • FIG. 2 is a high-resolution transmission electron microscope image of conductive composite particles produced in Example 1.
  • FIG. 2 It is the transmission electron micrograph and electron diffraction pattern of the electroconductive composite particle produced in Example 1.
  • FIG. 2 is an electron diffraction pattern of conductive composite particles produced in Example 1.
  • FIG. 3 It is the electron-beam diffraction pattern and analysis result of the electroconductive composite particle produced in Example 1.
  • FIG. 3 is a high-resolution transmission electron microscope image of conductive composite particles produced in Example 2.
  • FIG. It is the transmission electron micrograph and electron diffraction pattern of the electroconductive composite particle produced in Example 2.
  • FIG. 3 is an electron diffraction pattern of conductive composite particles produced in Example 2.
  • FIG. 4 is a high-resolution transmission electron microscope image of conductive composite particles produced in Example 3.
  • FIG. It is a transmission electron micrograph and electron beam diffraction pattern of the electroconductive composite particle produced in Example 3.
  • 4 is an electron diffraction pattern of conductive composite particles produced in Example 3.
  • FIG. It is an electron beam diffraction pattern and analysis result of the electroconductive composite particle produced in Example 3.
  • FIG. It is a schematic diagram for demonstrating the location measured in order to obtain
  • the conductive composite particle of the present embodiment is a conductive composite particle in which the surface of the titanium oxide particle is coated with a porous tin oxide fine particle layer, and in the high-resolution transmission electron microscope image, The length of the lattice image of tin oxide parallel to the lattice image of the titanium oxide is 80% or more with respect to the length of the lattice image of titanium oxide parallel to the surface.
  • tin oxide is used as tin oxide.
  • 30 g of titanium oxide particles are acid-washed with 0.05 to 0.2 M acid such as hydrochloric acid, nitric acid or sulfuric acid at 40 to 60 ° C. for 30 to 2 hours, followed by washing with water. If an acid of less than 0.05M is used in this acid cleaning, the conductive composite particles of this embodiment cannot be obtained.
  • 30 g of the titanium oxide particles are added to 800 g of water and heated and held at a temperature of 20 to 90 ° C. while stirring to disperse the titanium oxide particles uniformly, thereby preparing a dispersion containing titanium oxide particles.
  • an aqueous tin chloride solution in which SnCl 4 : 50 to 200 parts by mass and SbCl 3 : 2 to 25 parts by mass is added to 100 parts by mass of titanium oxide, and 10 to 35 wt%
  • An aqueous solution of sodium hydroxide is injected over 3 minutes to 2 hours while maintaining a pH of 3 to 9 at 20 to 80 ° C., and a coating layer made of Sb-containing tin hydroxide is deposited on the surface of the titanium oxide particles.
  • the titanium oxide particles having a coating layer made of Sb-containing tin hydroxide deposited on the surface are filtered off, and the obtained titanium oxide particles are washed and then kept in air at 500 to 1000 ° C. for 1 to 2 hours. By doing so, conductive composite particles can be obtained.
  • the aqueous solution of tin chloride is added to the dispersion containing titanium oxide particles, and then the aqueous solution of sodium hydroxide is injected. It may be injected.
  • a titanium oxide particle-containing dispersion was prepared without acid cleaning the titanium oxide particles, and then a coating layer made of Sb-containing tin hydroxide was deposited on the surface of the titanium oxide particles. Thereafter, conductive composite particles were produced by holding at a high temperature.
  • a second known technique there is a method for producing conductive composite particles that is different from the first known technique in that a dispersion containing titanium oxide particles to which a silane coupling agent is added is used. The method for producing conductive composite particles according to this embodiment described above is different from the first and second known techniques in that acid-washed titanium oxide particles are used.
  • FIG. 2 shows a scanning electron micrograph of conductive composite particles of Example 1 described later formed by the above-described method for manufacturing conductive composite particles according to the present embodiment.
  • FIG. 3 shows a transmission electron microscope photograph
  • FIG. 4 shows Ti mapping by an energy dispersive X-ray spectrometer (EDS) attached to the transmission electron microscope.
  • FIG. 5 shows Sn mapping by the same apparatus.
  • FIG. 2 shows that fine particles are present on the surface of the conductive composite particles 4. From FIG. 3, it can be seen that the fine particles are layered and exist on the surface of the conductive composite particles 4. Furthermore, it can be confirmed from FIGS. 4 and 5 that the tin oxide fine particle layer 6 exists on the surface of the titanium oxide particles 5.
  • FIG. 6 shows a transmission electron micrograph of the conductive composite particles 4 produced in Example 1
  • FIG. 7 shows a high-resolution transmission type in which the interface between the titanium oxide particles 5 and the tin oxide particles 6 is enlarged.
  • An electron microscope image is shown.
  • FIG. 7 shows that in the high-resolution transmission electron microscope image, the lattice image of titanium oxide parallel to the surface of the titanium oxide particles 5 and the lattice image of tin oxide are parallel.
  • FIG. 8 shows a high-resolution transmission electron microscope image in which the interface between the titanium oxide particles 5 and the tin oxide fine particles 6 of the conductive composite particles 4 produced in Comparative Example 1 described later is enlarged. From FIG.
  • the conductive composite particle 4 produced in Comparative Example 1 shows a lattice image of titanium oxide parallel to the surface of the titanium oxide particle 5 and a lattice image of tin oxide in a high-resolution transmission electron microscope image. However, it turns out that it is not parallel.
  • the length of the lattice image of titanium oxide parallel to the surface of the titanium oxide particles is The length of the tin oxide lattice image parallel to the titanium oxide lattice image is 80% or more. If the length of the tin oxide lattice image parallel to the lattice image of titanium oxide is less than 80%, the adhesion between the titanium oxide particles and the tin oxide fine particle layer decreases.
  • the titanium oxide has a rutile crystal structure and the tin oxide has a rutile crystal structure, that is, the phase in which the titanium oxide has a rutile crystal structure is the main phase.
  • the phase in which tin has a rutile crystal structure is preferably the main phase.
  • the mass ratio of the phase having a rutile type crystal structure in the titanium oxide particles may be 75 to 100%, and the tin oxide fine particle layer may be composed only of the phase having a rutile type crystal structure.
  • titanium oxide particles may be composed of a mixed phase of a stable phase having a rutile crystal structure and a metastable phase having an anatase crystal structure.
  • the (110) plane of the rutile crystal structure of titanium oxide and the (110) plane of the rutile crystal structure of tin oxide are preferably parallel. In this case, the mismatch between the crystal plane (crystal lattice) of titanium oxide and the crystal plane (crystal lattice) of tin oxide is small.
  • FIG. 10 shows a transmission electron micrograph and an electron beam diffraction pattern of the conductive composite particles 4 produced in Example 1.
  • the electron diffraction pattern of the portion surrounded by the white broken line A in the upper left transmission electron micrograph is shown in the upper right (TiO 2 / SnO 2 ).
  • An electron diffraction pattern of titanium oxide indicated by a black dot B in a white broken line A in the upper left transmission electron micrograph is shown in the lower left (TiO 2 ).
  • An electron diffraction pattern of tin oxide indicated by a white dot C in a white broken line A in the upper left transmission electron micrograph is shown in the lower right (SnO 2 ).
  • FIG. 11 shows an electron diffraction pattern of the conductive composite particles 4 produced in Example 1.
  • FIG. The electron diffraction patterns at the upper left, lower left, and lower right in FIG. 11 are the same as the electron diffraction patterns at the upper right, lower left, and lower right in FIG. 10, respectively.
  • the result of superposing the electron diffraction pattern of titanium oxide (lower left) and the electron diffraction pattern of tin oxide (lower right) is shown in the upper right of FIG. As can be seen from the upper right figure, there is almost no deviation between the electron diffraction pattern of titanium oxide and the electron diffraction pattern of tin oxide.
  • FIG. 12 shows an electron beam diffraction pattern and analysis results of the conductive composite particles 4 produced in Example 1.
  • the (110) plane of titanium oxide in the upper left of FIG. 12 and the diffraction pattern position due to the (110) plane of tin oxide in the upper right of FIG.
  • the (110) plane of the rutile crystal structure of titanium oxide and the (110) plane of the rutile crystal structure of tin oxide are shown on the electron diffraction pattern. It turns out that it is parallel.
  • the lower part of FIG. 12 describes that the (110) plane of titanium oxide and the (110) plane of tin oxide are parallel on the electron diffraction pattern.
  • FIG. 16 shows the electron diffraction pattern and analysis results of the conductive composite particles prepared in Example 2
  • FIG. 20 shows the electron diffraction pattern and analysis results of the conductive composite particles prepared in Example 3. Show.
  • the (110) plane of titanium oxide and the (110) plane of tin oxide are parallel on the electron diffraction pattern. 7 to 20, the observation is performed by adjusting the incident direction of the electron beam so that the diffraction point corresponding to the (110) plane is observed. For this reason, in any figure, it is observed that the (110) plane of titanium oxide and the (110) plane of tin oxide are parallel in the electron beam diffraction pattern.
  • the (110) plane of the rutile crystal structure of titanium oxide and the (110) plane of the rutile crystal structure of tin oxide are preferably parallel. In this case, the mismatch between the crystal plane (crystal lattice) of titanium oxide and the crystal plane (crystal lattice) of tin oxide is small.
  • the specific surface area of the titanium oxide particles used for producing the conductive composite particles of the present embodiment is preferably 1 to 10 m 2 / g. If it is less than 1 m 2 / g, it is difficult to increase the specific surface area of the conductive composite particles. If it exceeds 10 m 2 / g, the cohesive force of the titanium oxide particles becomes large, so that it becomes difficult to uniformly disperse the titanium oxide particles in the titanium oxide particle-containing dispersion in the above-described production process.
  • the crystal form of titanium oxide is not particularly limited, but is preferably a rutile type.
  • a rutile type In the anatase type and brookite type, it is difficult to deposit or form a tin oxide fine particle precursor on the surface of titanium oxide by a coprecipitation method or the like.
  • the tin oxide fine particle layer is porous. Thereby, electroconductivity can be provided to the titanium oxide particles, and platinum nanoparticles can be supported. Further, in the high-resolution transmission electron microscope image, since the lattice image of tin oxide in contact with the surface of the titanium oxide particles is parallel to the lattice image of the surface of the titanium oxide particles, the tin oxide fine particle layer and the titanium oxide layer High adhesion of particles.
  • the tin oxide is more preferably doped with Sb, P, F, Cl or the like. In this case, the conductivity and the like of the reduced tin oxide can be stabilized.
  • tin oxide is doped with Sb, from the viewpoint of conductivity, total SnO 2 and Sb: per 100 parts by weight, tin oxide, include many 15 parts by mass or less of Sb from 0 parts by weight Is preferred.
  • Sb is more than 15 parts by weight, there are problems that impurities are precipitated and the tin oxide fine particle layer is easily separated from the titanium oxide particles, and the platinum catalyst is hardly supported.
  • the quantitative analysis is performed for Sn and Sb by the ICP (inductively coupled plasma) method, assuming that all Sn is SnO 2 and all Sb is Sb. In this quantitative analysis, a measurement sample is prepared by dissolving tin oxide in sodium peroxide so that the Sn ion concentration becomes 1 to 100 ppm and then returning it to acidity.
  • the average particle diameter of the tin oxide fine particles constituting the tin oxide fine particle layer is preferably 3 to 20 nm.
  • the average particle diameter of the tin oxide fine particles is calculated from the observation result by TEM.
  • the tin oxide fine particle layer preferably has a thickness of 0.005 to 0.07 ⁇ m.
  • the thickness of the tin oxide fine particle layer is calculated from the observation result by TEM.
  • TEM observation a thin piece is prepared from an epoxy resin kneaded with conductive composite particles by mechanical polishing and ion polishing (Ion Polishing (IP) method or Cross-section Polishing (CP) method), and an electron beam is transmitted. Observe the region where the thickness is increased. For example, the particle diameter of about 50 conductive composite particles can be measured, and the average particle diameter can be obtained from the average value.
  • the thickness of the tin oxide fine particle layer can be measured for five conductive composite particles, and the thickness of the tin oxide fine particle layer can be obtained from the average value.
  • the number of conductive composite particles to be measured is not limited to this, and may be determined according to the magnification of the observation field.
  • the tin oxide fine particle layer is preferably 20 to 70 parts by mass with respect to 100 parts by mass of the conductive composite particles from the viewpoint of specific surface area and conductivity.
  • the BET specific surface area of the conductive composite particles is preferably 2 to 50 times the BET specific surface area of the titanium oxide particles from the viewpoint of an increase in the amount of platinum nanoparticles supported due to an increase in the specific surface area.
  • the green compact resistivity of the conductive composite particles is preferably less than 10,000 ⁇ ⁇ cm, and more preferably less than 10 ⁇ ⁇ cm.
  • the conductive composite particles according to the present embodiment as described above have high adhesion between the titanium oxide particle surface and the tin oxide fine particle layer, for example, even when mechanical alloying is used at the time of preparing the composition for the electrode catalyst layer, Can withstand mechanical shock.
  • composition for electrode catalyst layer of fuel cell contains the conductive composite particles and a dispersion medium.
  • the electrode catalyst layer is, for example, at least one catalyst layer selected from the group consisting of the fuel electrode catalyst layer 11 and the air electrode catalyst layer 31 as shown in FIG.
  • platinum nanoparticles may be supported on the conductive composite particles in the composition for the electrode catalyst layer. After the platinum nanoparticles are supported on the electrode catalyst layer, the electrode catalyst layer composition is preferred.
  • the method of supporting the platinum nanoparticles on the conductive composite particles is to add the platinum nanoparticle dispersion while stirring the solution in the solution in which the conductive composite particles are dispersed, and then dry the obtained liquid. It may be a known method such as.
  • the dispersion medium disperses the conductive composite particles and improves the film formability of the composition for the electrode catalyst layer.
  • the dispersion medium water and alcohols are preferable. Examples of alcohols include methanol and ethanol.
  • the content of the dispersion medium is preferably 50 to 99 parts by mass with respect to 100 parts by mass of the electrode catalyst layer composition.
  • the electrode catalyst layer composition preferably contains a binder.
  • the adhesive strength of the electrode catalyst layer composition can be increased by the binder.
  • the binder include polymer type binders such as acrylic resin, polycarbonate, and polyester, and non-polymer type binders such as metal soaps, metal complexes, metal alkoxides, and hydrolysates of metal alkoxides.
  • the binder content is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the electrode catalyst layer composition.
  • composition for an electrode catalyst layer may further contain an antioxidant, a leveling agent, a thixotropic agent, a filler, a stress relaxation agent, a conductive polymer, other additives, etc., as necessary, as long as the object of the present invention is not impaired. Can be blended.
  • the desired components including the conductive composite particles and the dispersion medium are mixed by a conventional method, for example, a paint shaker, ball mill, sand mill, centrimill, three rolls, etc.
  • a layer composition can be produced.
  • the composition for electrode catalyst layers can also be manufactured by normal stirring operation.
  • Electrode catalyst layer composition obtained as described above is wet-coated on a carrier tape or the like so as to have a desired thickness, then dried, and optionally fired, so that an electrode for a fuel cell is obtained.
  • a catalyst layer can be produced.
  • the electrode catalyst layer composition is wet-coated to a desired thickness on the electrolyte membrane or on the porous support layer that is a current collector, and then dried, In some cases, the electrode catalyst layer may be formed by firing.
  • the wet coating method is preferably, but not limited to, a spray coating method, a dispenser coating method, a knife coating method, a slit coating method, a doctor blade method, a screen printing method, an offset printing method, or a die coating method. Any method can be used.
  • the electrode catalyst layer of the fuel cell obtained by the above method contains conductive composite particles.
  • This conductive composite particle is composed of a tin oxide fine particle layer having resistance to oxidation and resistance to strong acid, and titanium oxide particles.
  • the tin oxide fine particle layer that supports the platinum nanoparticle catalyst has high adhesion to the titanium oxide particles and high resistance to carbon monoxide poisoning of platinum. For this reason, a highly reliable fuel cell can be manufactured by forming an electrode catalyst layer using the composition for electrode catalyst layers containing such electroconductive composite particles.
  • FIG. 1 shows an example of a schematic diagram of a cross-sectional structure of a fuel cell.
  • the fuel cell 1 has a configuration in which an electrolyte membrane 20 is sandwiched between a fuel electrode 10 and an air electrode 30.
  • the fuel electrode 10 includes a fuel electrode catalyst layer 11 and a porous support layer 12 that is a current collector.
  • the air electrode 30 includes an air electrode catalyst layer 31 and a porous support layer that is a current collector. 32.
  • the conductive composite particles contained in the electrode catalyst layers (11, 31) of the fuel cell 1 of the present embodiment are composed of a tin oxide fine particle layer having resistance to oxidation and resistance to strong acid, and inexpensive titanium oxide particles. ing. For this reason, the conductive composite particles are suitable for use in the air electrode catalyst layer 31. In addition, the conductive composite particles are suitable for the fuel electrode catalyst layer 11 because they have tin oxide fine particles effective for the carbon monoxide poisoning countermeasure of the platinum nanoparticle catalyst.
  • Examples of the fuel cell 1 include a polymer electrolyte fuel cell, a direct methanol fuel cell, and a phosphoric acid fuel cell.
  • the polymer electrolyte fuel cell in which the problem of carbon monoxide poisoning of the platinum nanoparticle catalyst is remarkable is more suitable as an application of the electrode catalyst layer of the present embodiment.
  • the fuel cell 1 is a polymer electrolyte fuel cell
  • a fluorine ion exchange membrane or the like is used as the electrolyte membrane 20
  • porous carbon paper or the like is used as the porous support layers 12 and 32.
  • the fuel cell 1 can be manufactured by laminating the porous support layer 12, the fuel electrode catalyst layer 11, the electrolyte membrane 20, the air electrode catalyst layer 31, and the porous support layer 32 in this order.
  • the conductive composite particles contained in the electrode catalyst layer (11, 31) of the obtained fuel cell 1 are composed of a tin oxide fine particle layer having resistance to oxidation and resistance to strong acid, and titanium oxide particles. And since the tin oxide fine particle layer which carries a platinum nanoparticle catalyst has high adhesiveness with a titanium oxide particle, and the tolerance with respect to carbon monoxide poisoning of platinum is high, the fuel cell of this embodiment has high reliability.
  • Titanium chemical titanium oxide particles having a specific surface area of 5 m 2 / g (TiO 2 particles whose surface is not modified and whose phase is a rutile crystal structure is the main phase) are mixed with 0.1 M hydrochloric acid at 50 ° C. An acid wash for 1 hour was performed, followed by a water wash. Water: to 800 cm 3, the titanium oxide particles: 30 g was added, temperature was stirred at 90 ° C. was heated held with, uniformly dispersing titanium oxide particles in water was prepared containing titanium oxide particles dispersion.
  • the titanium oxide particles having a coating layer made of Sb-containing tin hydroxide deposited on the surface were separated by filtration and washed. Thereafter, the titanium oxide particles having a coating layer made of Sb-containing tin hydroxide deposited on the surface thereof were kept in the air at 500 ° C. for 2 hours, whereby the conductive composite particles of Example 1 (Sb content: 5 mass). %).
  • the content of Sb was calculated on the assumption that all of the raw material SnCl 4 was SnO 2 and SbCl 3 was all Sb.
  • the Sb content is the same in other examples and comparative examples.
  • Titanium oxide particle-containing dispersion was prepared using Sakai Chemical Titanium Oxide Particles having a specific surface area of 1 m 2 / g. Water: 200 cm 3 dissolved SnCl 4 : 40 g and SbCl 3 : 2.1 g.
  • the conductive composite of Example 2 was prepared in the same manner as in Example 1, except that an aqueous tin solution was prepared and that the time for dropping the aqueous tin chloride solution and the aqueous sodium hydroxide solution to the titanium oxide particle-containing dispersion was 1 hour. Particles (Sb content: 5% by mass) were obtained.
  • Example 3 Water: SnCl 4 : 40 g and SbCl 3 : 2.1 g were dissolved in 200 cm 3 to prepare a tin chloride aqueous solution, and the time for dropping the tin chloride aqueous solution and the sodium hydroxide aqueous solution to the titanium oxide particle-containing dispersion was 3 minutes.
  • Example 1 except that the titanium oxide particles having a coating layer made of Sb-containing tin hydroxide deposited on the surface thereof (filtered and washed) were kept in nitrogen at 1000 ° C. for 1 hour. In the same manner as in Example 1, conductive composite particles of Example 3 (Sb content: 5% by mass) were obtained.
  • this titanium oxide particle-containing dispersion was mixed with a tin chloride aqueous solution in which SnCl 4 : 40 g and SbCl 3 : 2.1 g were dissolved in water: 200 cm 3 , and a 35 wt% sodium hydroxide aqueous solution.
  • the mixture was added dropwise over 0.5 hours so as to maintain the temperature in the range of 3 ° C. and pH 3 to 9 to cause hydrolysis.
  • a white slurry containing titanium oxide particles on which a coating layer made of Sb-containing tin hydroxide was deposited was obtained.
  • the titanium oxide particles having a coating layer made of Sb-containing tin hydroxide deposited on the surface were separated by filtration and washed. Thereafter, the titanium oxide particles having a coating layer made of Sb-containing tin hydroxide deposited on the surface thereof are kept in air at 500 ° C. for 2 hours, whereby the conductive composite particles of Comparative Example 1 (Sb content: 5 mass). %).
  • the titanium oxide particles having a coating layer made of Sb-containing tin hydroxide deposited on the surface were separated by filtration and washed. Thereafter, the titanium oxide particles having a coating layer made of Sb-containing tin hydroxide deposited on the surface are kept in air at 400 ° C. for 2 hours, whereby the conductive composite particles of Comparative Example 2 (Sb content: 5 mass). %).
  • Comparative Example 3 A titanium oxide particle-containing dispersion having a specific surface area of 5 m 2 / g was subjected to acid cleaning with 0.001M hydrochloric acid at 20 ° C. for 0.5 hour, and then the titanium oxide particle-containing dispersion without water washing. The same as in Example 1 except that the temperature at which the titanium oxide particles (the one filtered and washed) on which the coating layer made of Sb-containing tin hydroxide was deposited was 400 ° C. was prepared. Thus, conductive composite particles of Comparative Example 3 (Sb content: 5% by mass) were obtained.
  • Example 1 The conductive composite particles produced in Example 1 were observed with a scanning electron microscope (model number: ULTRA55) manufactured by Carl Zeiss (FIG. 2). Next, the conductive composite particles produced in Example 1 were observed with a transmission electron microscope (model number: JEM-2010F) manufactured by JEOL, and a transmission electron micrograph of the conductive composite particles was taken (FIG. 3, FIG. 3). 6). Moreover, Ti mapping and Sn mapping were performed using the EDS attached to the transmission electron microscope with the same field of view (the same field of view as FIG. 3) as the field of view of the transmission electron micrograph (FIGS. 4 and 5).
  • the conductive composite particles produced in Examples 1 to 3 and Comparative Examples 1 and 3 were observed with a high-resolution transmission electron microscope (model number: CM20) manufactured by FEI, and a high-resolution transmission electron microscope image was obtained ( 7-9, 13, 17).
  • the length of the tin lattice image was measured.
  • the lattice image of titanium oxide parallel to the surface of the titanium oxide particles is the center of the interface between the titanium oxide particles and the tin oxide fine particles in the high resolution transmission electron microscope image.
  • the surface of the titanium oxide particles (that is, the interface between the titanium oxide particles and the tin oxide fine particles) and the interface between the titanium oxide particles and the tin oxide fine particles are 4 to
  • a line connecting points where the contrast of the region representing titanium oxide changes to the contrast of the region representing tin oxide fine particles is represented by an interface between the titanium oxide particles and the tin oxide fine particles (oxidation). Surface of titanium particles).
  • the crystal orientation in which the lattice image (lattice stripe) is observed is tilted with respect to the surface of the titanium oxide particles, or if the surface of the titanium oxide particles is uneven, the oxidation observed with a high-resolution transmission electron microscope image
  • the interface between the titanium particles and the tin oxide fine particles may be uneven.
  • the center of the interface is the midpoint between the peak of the interface peak and the peak of the valley.
  • the lattice image of tin oxide parallel to the lattice image of titanium oxide in the high resolution transmission electron microscope image is the same as the interface between the titanium oxide particle and the tin oxide fine particle in the high resolution transmission electron microscope image.
  • Example 1 in the high-resolution transmission electron microscope image of Example 1 shown in FIG. 7, from the center of the interface between the titanium oxide particles and the tin oxide fine particles, the width parallel to the interface: 50 nm, the thickness: A 5 nm region was determined. Within this region, the absolute value of the angle formed between the surface of the titanium oxide particles and the lattice image of the fourth to eighth layers of titanium oxide from the interface between the titanium oxide particles and the tin oxide fine particles was measured. Further, in the same region, a lattice image of the fourth layer titanium oxide from the interface between the titanium oxide particles and the tin oxide fine particles and a lattice image of the fourth layer tin oxide from the interface between the titanium oxide particles and the tin oxide fine particles are formed.
  • the absolute value of the angle was measured. Similarly, the lattice image of the fifth to eighth layers of titanium oxide from the interface between the titanium oxide particles and the tin oxide fine particles, and the lattice image of the fifth to eighth layers of tin oxide from the interface between the titanium oxide particles and the tin oxide fine particles. The absolute value of the angle formed by each was measured.
  • the titanium oxide is within the width: 50 nm, thickness: 5 nm region parallel to the interface from the center of the interface between the titanium oxide particles and the tin oxide fine particles.
  • the lattice image of the fourth layer of tin oxide from the interface between the titanium oxide particles and the tin oxide fine particles and the lattice image of the fourth layer of titanium oxide from the interface between the titanium oxide particles and the tin oxide fine particles.
  • the length (Ls) of the lattice image of tin oxide having an absolute angle value of 10 ° or less was measured. [(Ls / Lt) ⁇ 100] was calculated from the obtained Lt and Ls.
  • the lattice of the fifth to eighth layers of titanium oxide from the interface between the titanium oxide particles and the tin oxide fine particles the lattice of the fifth to eighth layers of tin oxide from the interface between the titanium oxide particles and the tin oxide fine particles.
  • the length (Ls) of the lattice image of tin oxide having an absolute value of 10 ° or less with the image was measured.
  • the fourth layer of the lattice image of titanium oxide, the fourth layer of the lattice image of tin oxide, the fifth layer of the lattice image of titanium oxide, and the fifth layer of the lattice image of tin oxide. [(Ls / Lt) ⁇ 100] was calculated using the measured Ls and Lt.
  • FIG. 21 is a schematic diagram for explaining a location measured for obtaining (Ls / Lt) ⁇ 100].
  • 4 to 8 layers from the interface between the titanium oxide particles and the tin oxide fine particles such as the fourth layer of SnO 2 and the fourth layer of TiO 2 , the fifth layer of SnO 2 and the fifth layer of TiO 2.
  • Ls and Lt were measured for each layer, [(Ls / Lt) ⁇ 100] was calculated, and the average was obtained.
  • the BET specific surface area of the conductive composite particles produced in Examples 1 to 3, Comparative Examples 1 to 3, and Reference Examples 1 and 2 was measured.
  • the BET specific surface area was measured by a BET method based on nitrogen adsorption, using 1.0 g of the conductive composite particles produced in each example, using a nitrogen adsorption measuring device (model number: AUTOSORB-1) manufactured by QUANTACHROME.
  • the powder resistivity of the conductive composite particles produced in Examples 1 to 3, Comparative Examples 1 to 3, and Reference Examples 1 and 2 was measured using a powder resistance measurement system (model number: MCP-PD51) manufactured by Mitsubishi Chemical Analytic.
  • the sample mass (the mass of the conductive composite particles to be measured) was 5.0 g, and measurement was performed under a pressure of 9.8 MPa.
  • the relatively dark region in the tin oxide fine particle layer in the scanning electron microscope image was a region where the tin oxide fine particles were peeled off. Then, the area of the region judged to be peeled in the scanning electron microscope image was obtained, and this area was divided by the area of the tin oxide fine particles in the same scanning electron microscope image, and the value was seen to peel. The ratio was tin oxide fine particles.
  • the X-ray diffraction patterns of the conductive composite particles prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were measured with a Bruker X-ray diffractometer (model number: MXP-18VAHF). From the obtained X-ray diffraction patterns The crystal structure was identified. In the measurement, the step width was set so that the step width was about 1 ⁇ 4 of the half width, and the integration time was set so that the main peak was 10000 cps or more.
  • the conductive composite particles produced in Examples 1 to 3 were observed with a transmission electron microscope (model number: CM20) manufactured by JEOL, and transmission electron micrographs and electron beam diffraction patterns of the conductive composite particles were obtained (Fig. 10-12, 14-16, 18-20).
  • An electron beam diffraction pattern was obtained by adjusting the incident direction of the electron beam so that the beam diameter of the electron beam was about 1 mm and a diffraction point in the [110] direction was observed.
  • FIG. 2 shows a scanning electron micrograph of the conductive composite particles produced in Example 1. Further, FIG. 3 shows a transmission electron micrograph of the conductive composite particles produced in Example 1, FIG. 4 shows Ti mapping by EDS attached to the transmission electron microscope, and FIG. 5 shows Sn mapping by the apparatus. 2 to 5, it was found that the surface of the titanium oxide particles of the conductive composite particles was coated with a porous tin oxide fine particle layer.
  • FIG. 6 shows a transmission electron micrograph of the conductive composite particles produced in Example 1
  • FIG. 7 shows a high-resolution transmission electron microscope image in which the interface between the titanium oxide particles and the tin oxide fine particles is enlarged. Indicates.
  • the high-resolution transmission electron microscope image shown in FIG. 7 from the center of the interface between the titanium oxide particles and the tin oxide fine particles, within the region of width: 50 nm and thickness: 5 nm parallel to the interface, The presence of a lattice image of titanium oxide having an absolute value of 10 ° or less, that is, a lattice image of titanium oxide parallel to the surface of the titanium oxide particle, is expressed in 4 to 8 layers from the interface between the titanium oxide particle and the tin oxide fine particle.
  • the titanium oxide is within the width: 50 nm, thickness: 5 nm region parallel to the interface from the center of the interface between the titanium oxide particles and the tin oxide fine particles.
  • the lattice image of the fourth to eighth layer tin oxide from the interface between the titanium oxide particles and the tin oxide fine particles, and the fourth to eighth layer titanium oxides from the interface between the titanium oxide particles and the tin oxide fine particles was measured.
  • the fourth layer of titanium oxide and the fourth layer of tin oxide, the fifth layer of titanium oxide, and the fifth layer of tin oxide are associated with Ls and Lt for each layer [(Ls / Lt ) ⁇ 100] and the average was obtained.
  • Table 1 shows Ls, Lt, [(Ls / Lt) ⁇ 100] of each layer of the conductive composite particles produced in Example 1, and an average value thereof. As can be seen from Table 1, [(Ls / Lt) ⁇ 100] was 80% or more. Table 2 also shows the average value of [(Ls / Lt) ⁇ 100] of the conductive composite particles prepared in Examples 1 to 3, Comparative Examples 1 to 3, and Reference Examples 1 and 2. Table 2 also shows the state of the tin oxide fine particles on the surface of the titanium oxide particles and the state of the tin oxide fine particle layer (whether it is porous or not). Table 2 shows the results of the BET specific surface area, the green compact resistivity, and the adhesion of the conductive composite particles produced in Example 1.
  • FIG. 9 shows a high-resolution transmission electron microscope image of the conductive composite particles produced in Example 1. In the high-resolution transmission electron microscope image shown in FIG.
  • the above oxidation is performed in the region of width: 50 nm and thickness: 5 nm parallel to the interface from the center of the interface between the titanium oxide particles and the tin oxide fine particles.
  • the absolute value of the angle formed with the lattice image of titanium is 10 ° or less, that is, the presence of the lattice image of tin oxide parallel to the lattice image of titanium oxide is 4 from the interface between the titanium oxide particles and the tin oxide fine particles.
  • the lattice images of all the tin oxides in the eighth to eighth layers were confirmed.
  • FIG. 10 shows a transmission electron micrograph and an electron diffraction pattern of the conductive composite particles produced in Example 1.
  • the electron diffraction pattern of the portion surrounded by the white broken line A in the upper left transmission electron micrograph is shown in the upper right (TiO 2 / SnO 2 ).
  • region and angle which contain a tin oxide fine particle, a titanium oxide particle, and these interfaces, and can obtain an electron beam diffraction pattern were selected as an area
  • an electron beam diffraction pattern of titanium oxide indicated by a black dot B in a white broken line A in the upper left transmission electron micrograph is shown in the lower left (TiO 2 ).
  • FIG. 11 shows an electron diffraction pattern of the conductive composite particles produced in Example 1.
  • the electron diffraction patterns at the upper left, lower left, and lower right in FIG. 11 are the same as the electron diffraction patterns at the upper right, lower left, and lower right in FIG. 10, respectively.
  • the result of superimposing the electron diffraction pattern of titanium oxide (lower left) and the electron diffraction pattern of tin oxide (lower right) on the upper right of FIG. 11 is shown.
  • FIG. 12 shows an electron beam diffraction pattern and analysis results of the conductive composite particles produced in Example 1.
  • the crystal structure of titanium oxide and tin oxide is known to be tetragonal (rutile type) by X-ray diffraction
  • the electron diffraction pattern of titanium oxide left
  • Indexing was performed on the electron diffraction pattern (right) of tin oxide.
  • FIG. 11 and FIG. 12 when the electron diffraction pattern of tin oxide and the electron diffraction pattern of titanium oxide are superimposed (upper right of FIG. 11), the (110) plane of the rutile crystal structure of titanium oxide.
  • the (110) plane of titanium oxide and the (110) plane of tin oxide are It was found to be parallel on the electron diffraction pattern.
  • the (112) plane of titanium oxide and the (112) plane of tin oxide are parallel on the electron diffraction pattern, and the (111) plane of titanium oxide and the (111) plane of tin oxide.
  • the electron diffraction pattern is parallel on the electron diffraction pattern.
  • FIG. 22 illustrates that the (110) plane of the rutile crystal structure of titanium oxide and the (110) plane of the rutile crystal structure of tin oxide are parallel on the electron diffraction pattern. The figure is shown.
  • the right diagram in FIG. 22 is an analysis of the electron diffraction pattern at the upper right in FIG.
  • the diffraction of [110] starts from a direct spot.
  • a straight line passing through the first and second diffraction points counted from the direct spot in the [110] direction so as to pass through the point was used as a reference line in the [110] direction.
  • the reference line is an intermediate point between the two diffraction points derived from TiO 2 and SnO 2. I tried to pass.
  • the direct spot (white point in the solid circle on the right in FIG. 22) starts from the direct spot and passes through the diffraction spot [110].
  • 110] direction straight lines passing through the first and second diffraction spots were drawn.
  • This straight line was used as a reference line in the [110] direction (solid line with an arrow on the right in FIG. 22). From this reference line, a boundary line (a broken line with two arrows on the right side of FIG. 22) of ⁇ 5 ° was drawn starting from the direct spot.
  • the third and fourth diffraction points counted in the [110] direction from the direct spot are present inside the two boundary lines (on the reference line side). It was determined that the [110] direction of the rutile-type crystal structure and the [110] direction of the rutile-type crystal structure of tin oxide were parallel on the electron diffraction pattern. In the rutile crystal structure, the [110] direction is perpendicular to the (110) plane. Therefore, in the right diagram of FIG. 22, the [110] direction of the rutile crystal structure of titanium oxide and the [110] direction of the rutile crystal structure of tin oxide are parallel in the electron diffraction pattern. The (110) plane of the rutile crystal structure of titanium oxide and the (110) plane of the rutile crystal structure of tin oxide were also judged to be parallel in the electron diffraction pattern.
  • the width parallel to the interface is 50 nm and the thickness is 5 nm from the center of the interface between the titanium oxide particles and the tin oxide fine particles.
  • the absolute value of the angle formed with the lattice image of titanium oxide is 10 ° or less, that is, the presence of the lattice image of tin oxide parallel to the lattice image of titanium oxide is expressed as follows: All the lattice images of tin oxide in the 4th to 8th layers from the interface were confirmed. And similarly to Example 1, the average value of [(Ls / Lt) ⁇ 100] of the conductive composite particles was calculated.
  • Table 2 shows [(Ls / Lt) ⁇ 100] of the conductive composite particles produced in Example 2, the state of the tin oxide fine particles on the surface of the titanium oxide particles, the state of the tin oxide fine particle layer, the BET specific surface area, the pressure. The results of powder resistivity and adhesion are shown.
  • Table 3 shows the results of X-ray diffraction of the conductive composite particles produced in Example 2.
  • FIGS. 9 to 12 of Example 1 the results of the same analysis as in FIGS. 9 to 12 of Example 1 for the conductive composite particles produced in Example 2 are shown in FIGS.
  • the (110) plane of titanium oxide and the (110) plane of tin oxide were parallel on the electron diffraction pattern.
  • the (332) plane of titanium oxide and the (332) plane of tin oxide are parallel on the electron diffraction pattern
  • the (113) plane of titanium oxide and the (113) plane of tin oxide are on the electron diffraction pattern. It turned out to be parallel.
  • the width parallel to the interface is 50 nm and the thickness is 5 nm from the center of the interface between the titanium oxide particles and the tin oxide fine particles.
  • the absolute value of the angle formed with the lattice image of titanium oxide is 10 ° or less, that is, the presence of the lattice image of tin oxide parallel to the lattice image of titanium oxide is defined as the interface between the titanium oxide particle and the tin oxide fine particle interface.
  • Table 2 shows [(Ls / Lt) ⁇ 100] of the conductive composite particles produced in Example 3, the state of the tin oxide fine particles on the surface of the titanium oxide particles, the state of the tin oxide fine particle layer, the BET specific surface area, the pressure. The results of powder resistivity and adhesion are shown. Table 3 shows the results of X-ray diffraction of the conductive composite particles produced in Example 3.
  • FIG. 8 shows a high-resolution transmission electron microscope image in which the interface between the titanium oxide particles and the tin oxide particles of the conductive composite particles produced in Comparative Example 1 is enlarged.
  • the width parallel to the interface 50 nm
  • the thickness In the region of 5 nm, the absolute value of the angle formed between the surface of the titanium oxide particles and the lattice image of the fourth to eighth layers of titanium oxide from the interface between the titanium oxide particles and the tin oxide fine particles is smaller than 10 °.
  • the lattice image of titanium oxide was parallel to the surface.
  • Table 2 shows the results of the state of the tin oxide fine particles, the state of the tin oxide fine particle layer, the BET specific surface area, the green compact resistivity, and the adhesion on the surface of the titanium oxide particles of the conductive composite particles prepared in Comparative Example 1. Show.
  • Table 3 shows the results of X-ray diffraction of the conductive composite particles produced in Comparative Example 1.
  • Table 2 shows the results of the state of the tin oxide fine particles, the state of the tin oxide fine particle layer, the BET specific surface area, the green compact resistivity, and the adhesion on the surface of the titanium oxide particles of the conductive composite particles prepared in Comparative Example 1. Show.
  • Table 3 shows the results of X-ray diffraction of the conductive composite particles produced in Comparative Example 2.
  • the absolute value of the angle formed with the lattice image of titanium oxide is 10 ° or less, that is, the presence of the lattice image of tin oxide parallel to the lattice image of titanium oxide is 4 from the interface between the titanium oxide particles and the tin oxide fine particles.
  • Table 2 shows [(Ls / Lt) ⁇ 100] of the conductive composite particles prepared in Comparative Example 3, the state of the tin oxide fine particles on the surface of the titanium oxide particles, the state of the tin oxide fine particle layer, the BET specific surface area, the pressure. The results of powder resistivity and adhesion are shown. Table 3 shows the results of X-ray diffraction of the conductive composite particles produced in Comparative Example 3.
  • Table 2 shows the BET specific surface area of the titanium oxide particles of Reference Example 1, the BET specific surface area of the tin oxide particles of Reference Example 2, and the green compact resistivity.
  • the green compact resistivity in Reference Example 1 was outside the measurement range of the powder resistance measurement system.
  • Examples 1 to 3 show high resolution transmission electron images in the lattice image of titanium oxide in contrast to the lattice image of titanium oxide parallel to the surface of the titanium oxide particles in high resolution transmission electron microscope images.
  • the ratio of the length of the lattice image of tin oxide parallel to the microscopic image [(Ls / Lt) ⁇ 100] was 80% or more, and the adhesion between the tin oxide fine particle layer and the titanium oxide particles was high.
  • the tin oxide fine particle layer was porous, the BET specific surface area was very large, the green compact resistivity was low, and the conductivity was high. Therefore, it was found that any of the conductive composite particles produced in Examples 1 to 3 was suitable as a support for supporting the platinum nanoparticle catalyst.
  • the titanium oxide particles in the high-resolution transmission electron microscope image The lattice image of tin oxide was not parallel to the lattice image of titanium oxide parallel to the surface, and adhesion was not good.
  • the film-form tin oxide fine particle which is not porous peeled from the titanium oxide particle is not porous peeled from the titanium oxide particle.
  • Reference Example 1 using titanium oxide particles had no conductivity.
  • Reference Example 2 using tin oxide fine particles aggregation was severe and handling properties were poor. Therefore, it was found that Comparative Examples 1 to 3 and Reference Examples 1 and 2 are not suitable as carriers for supporting the platinum nanoparticle catalyst.
  • the conductive composite particles of the present invention a tin oxide fine particle layer having high adhesion to the titanium oxide powder and a large specific surface area is formed on the surface of the titanium oxide particles. Moreover, the electroconductive composite particle of this invention has high electroconductivity. For this reason, the electroconductive composite particle of this invention is suitable for the support

Abstract

L'invention concerne notamment des particules composites conductrices dont chacune comporte une particule d'oxyde de titane et une couche poreuse de microparticules d'oxyde d'étain qui recouvre la surface de la particule d'oxyde de titane, caractérisée en ce que, dans une micrographie électronique par transmission à haute résolution, la longueur d'une image du réseau d'oxyde d'étain parallèle à un image du réseau d'oxyde de titane qui est parallèle à la surface de la particule d'oxyde de titane représente au moins 80% de la longueur de l'image du réseau d'oxyde de titane.
PCT/JP2014/074292 2013-09-12 2014-09-12 Particules composites conductrices, composition pour couche de catalyseur d'électrode pour pile à combustible, couche de catalyseur d'électrode pour pile à combustible, et pile à combustible WO2015037721A1 (fr)

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