WO2023218790A1 - Support de catalyseur pour piles à combustible, catalyseur pour piles à combustible, couche de catalyseur d'électrode et pile à combustible - Google Patents

Support de catalyseur pour piles à combustible, catalyseur pour piles à combustible, couche de catalyseur d'électrode et pile à combustible Download PDF

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WO2023218790A1
WO2023218790A1 PCT/JP2023/012971 JP2023012971W WO2023218790A1 WO 2023218790 A1 WO2023218790 A1 WO 2023218790A1 JP 2023012971 W JP2023012971 W JP 2023012971W WO 2023218790 A1 WO2023218790 A1 WO 2023218790A1
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fuel cell
carbon black
less
catalyst layer
electrode catalyst
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PCT/JP2023/012971
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English (en)
Japanese (ja)
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哲哉 伊藤
祐作 原田
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デンカ株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a fuel cell catalyst carrier, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell.
  • fuel cells having a cell structure of separator/gas diffusion layer/electrode catalyst layer/electrolyte membrane/electrode catalyst layer/gas diffusion layer/separator have been used as polymer electrolyte fuel cells.
  • the electrode catalyst layer for example, a layer in which carbon black carrying metal particles such as platinum particles is dispersed in an electrolyte is used.
  • a method for efficiently dispersing carbon black in an electrode catalyst layer for example, a first step of mixing catalyst-supported carbon black, an ion exchange resin, and a solvent and externally shearing the mixture with an external shearer, and an internal shearer
  • a method for producing a catalyst paste for a fuel cell which includes a second step of performing internal shearing (liquid-liquid shearing), and a third step of performing external shearing again.
  • the metal particles in the electrode catalyst layer have high catalytic activity per unit mass (reaction efficiency of the electrode catalyst layer).
  • the present invention relates to, for example, the following ⁇ 1> to ⁇ 8>.
  • ⁇ 1> A fuel cell catalyst carrier made of carbon black, The specific surface area is 170 m 2 /g or more and 400 m 2 /g or less, The ratio (S 2 /S 1 ) of the peak area (S 1 ) of the m/z 57 peak to the peak area (S 2 ) of the m/z 128 peak detected by temperature programmed desorption gas analysis is 2.00. is less than Support for catalysts for fuel cells.
  • ⁇ 2> As described in ⁇ 1>, when a 3% by mass slurry is prepared using N-methyl-2-pyrrolidone as a dispersion medium, the slurry viscosity at 25°C and a shear rate of 10 s -1 is 400 mPa s or more and 1500 mPa s or less.
  • catalyst carrier for fuel cells ⁇ 3> The fuel cell catalyst carrier according to ⁇ 1> or ⁇ 2>, which has a hydrochloric acid absorption amount of 39 mL/5 g or more.
  • ⁇ 4> The fuel cell catalyst carrier according to any one of ⁇ 1> to ⁇ 3>, which has a DBP absorption amount of 200 mL/100 g or more and 400 mL/100 g or less.
  • a fuel cell catalyst comprising at least one metal particle selected from the group consisting of platinum particles and platinum alloy particles supported on the fuel cell catalyst carrier according to any one of ⁇ 1> to ⁇ 4>.
  • ⁇ 7> A fuel cell comprising the electrode catalyst layer according to ⁇ 6>.
  • ⁇ 8> comprising a first separator, a first gas diffusion layer, an anode electrode catalyst layer, an electrolyte membrane, a cathode electrode catalyst layer, a second gas diffusion layer, and a second separator, A fuel cell, wherein at least one of the anode electrode catalyst layer and the cathode electrode catalyst layer is the electrode catalyst layer according to ⁇ 6>.
  • a carrier for a fuel cell catalyst is provided that can realize a fuel cell catalyst that can achieve both high dispersibility and high reaction efficiency. Further, according to the present invention, a fuel cell catalyst is provided that is capable of achieving both high dispersibility and high reaction efficiency. Furthermore, according to the present invention, an electrode catalyst layer and a fuel cell containing the above fuel cell catalyst are provided.
  • FIG. 2 is a diagram showing a chart of m/z 57 and m/z 128 of carbon black used in Example 1, detected by temperature-programmed desorption gas analysis.
  • a numerical range indicated using “ ⁇ ” means a range from “more than” the number on the left side to “less than” the number on the right side.
  • a to B means greater than or equal to A and less than or equal to B.
  • the fuel cell catalyst carrier of this embodiment is made of carbon black, and is a carrier that forms a fuel cell catalyst by supporting metal particles, which will be described later.
  • the fuel cell catalyst carrier (hereinafter also simply referred to as carbon black) of the present embodiment has a specific surface area of 170 m 2 /g or more and 400 m 2 /g or less.
  • the reaction efficiency can be determined by comparing the level of voltage at the same current value in the current potential curve in fuel cell evaluation, and it can be said that the higher the voltage, the higher the reaction efficiency.
  • the specific surface area is 180 m 2 /g or more, 190 m 2 /g or more, 200 m 2 /g or more, 210 m 2 /g or more, 220 m 2 /g or more, or 230 m 2 /g or more.
  • the catalyst paste which is a mixture of a fuel cell catalyst, an electrolyte, and a solvent, tends to become non-uniform, and in the electrode catalyst layer obtained by coating the catalyst paste, the fuel cell catalyst tends to form agglomerated particles. Agglomerated particles in the electrode catalyst layer cause protrusions and may damage the electrolyte membrane-electrode assembly (MEA). Further, when the fuel cell catalyst aggregates in the electrode catalyst layer, the contact area between the gas and the metal particles becomes smaller, and the reaction efficiency decreases.
  • MEA electrolyte membrane-electrode assembly
  • the specific surface area is 400 m 2 /g or less, a uniform catalyst paste is easily obtained, an electrode catalyst layer with few aggregated particles is easily obtained, and long-term reliability and reaction efficiency are improved. From the viewpoint of achieving the above effects more significantly, the specific surface area may be 395 m 2 /g or less, or 390 m 2 /g or less.
  • the specific surface area is, for example, 170 to 400 m 2 /g, 170 to 395 m 2 /g, 170 to 390 m 2 /g, 180 to 400 m 2 /g, 180 to 395 m 2 /g, 180 to 390 m 2 /g, 190 ⁇ 400m 2 /g, 190 ⁇ 395m 2 /g, 190 ⁇ 390m 2 /g, 200 ⁇ 400m 2 /g, 200 ⁇ 395m 2 /g, 200 ⁇ 390m 2 /g, 210 ⁇ 400m 2 /g, 210 ⁇ 395m 2 /g, 210-390m 2 /g, 220-400m 2 /g, 220-395m 2 /g, 220-390m 2 /g, 230-400m 2 /g, 230-395m 2 /g or 230-390m 2 /g.
  • the ratio (S 2 /S 1 ) is less than 2.00.
  • the ratio (S 2 /S 1 ) indicates the ratio of organic components present on the surface of the carbon black, for example, the ratio of polycyclic aromatic hydrocarbons to aliphatic hydrocarbons.
  • m/z is a symbol that means the value on the horizontal axis of a mass spectrum.
  • the number to the right of m/z is the value (dimensionless quantity) obtained by dividing the mass of the target ion by the unified atomic mass unit and further dividing by the number of charges on the ion.
  • the peak position in the mass spectrum is indicated together with z.
  • the ratio (S 2 /S 1 ) can be determined by evolved gas mass spectrometry (EGA-MS). Specifically, carbon black was set in a gas chromatograph mass spectrometer equipped with a pyrolysis device, held at 50°C for 5 minutes in an atmospheric pressure He flow, and then heated to 800°C at a rate of 80°C/min. do. Perform mass spectrometry of the components desorbed by increasing the temperature under the following conditions, and calculate the ratio of the peak area (S 1 ) of the peak at m/z 57 to the peak area (S 2 ) of the peak at m/z 128. Then, the ratio (S 2 /S 1 ) is calculated.
  • EVA-MS evolved gas mass spectrometry
  • the peak area refers to the peak area of a component (component corresponding to m/z 57 or m/z 128) detected by desorption from carbon black due to temperature elevation in the temperature programmed desorption gas analysis method.
  • the present inventors found that in carbon black having a high specific surface area, the surface properties analyzed by temperature-programmed desorption gas analysis are determined by the number of aggregated particles in the electrode catalyst layer. was found to have a significant influence on That is, the carbon black of this embodiment has a ratio (S 2 /S 1 ) of less than 2.00, so that it can achieve a sufficiently low number of aggregated particles for practical use while having a high specific surface area.
  • the detected peak at m/z 128 is a peak derived from polycyclic aromatic hydrocarbons typified by naphthalene, and the peak at m/z 57 is a peak derived from aliphatic hydrocarbons. That is, a small ratio (S 2 /S 1 ) means that the proportion of polycyclic aromatic hydrocarbons present on the carbon black surface is small.
  • the ratio (S 2 /S 1 ) by setting the ratio (S 2 /S 1 ) to be less than 2.00, even carbon black with a developed structure and a high specific surface area is difficult to aggregate in the electrode catalyst layer and is not formed into aggregated particles. The resulting decrease in reaction efficiency and reliability can be suppressed. In addition, a uniform electrode catalyst layer is easily obtained, local variations in catalyst efficiency are suppressed, and a fuel cell with a high output voltage and long life is easily obtained.
  • the ratio (S 2 /S 1 ) is less than 2.00 in order to sufficiently reduce the number of aggregated particles in the electrode catalyst layer. This is desirable.
  • the ratio (S 2 /S 1 ) is less than 1.80, less than 1.60, less than 1.40, less than 1.20, less than 1.00, and 0. It may be less than .80, less than 0.60 or less than 0.50.
  • the lower limit of the ratio (S 2 /S 1 ) is not particularly limited, but from the viewpoint of excellent productivity, the ratio (S 2 /S 1 ) should be 0.05 or more, 0.10 or more, or 0.20 or more. It's fine. That is, the ratio (S 2 /S 1 ) is, for example, 0.05 or more and less than 2.00, 0.05 or more and less than 1.80, 0.05 or more and less than 1.60, 0.05 or more and less than 1.40, and 0. .05 or more and less than 1.20, 0.05 or more and less than 1.00, 0.05 or more and less than 0.80, 0.05 or more and less than 0.60, 0.05 or more and less than 0.50, 0.10 or more2.
  • 0.10 or more and less than 1.80 0.10 or more and less than 1.60, 0.10 or more and less than 1.40, 0.10 or more and less than 1.20, 0.10 or more and less than 1.00, 0. 10 or more and less than 0.80, 0.10 or more and less than 0.60, 0.10 or more and less than 0.50, 0.20 or more and less than 2.00, 0.20 or more and less than 1.80, 0.20 or more and less than 1.60 less than 0.20 or more, less than 1.40, 0.20 or more and less than 1.20, 0.20 or more and less than 1.00, 0.20 or more and less than 0.80, 0.20 or more and less than 0.60, or 0.20 It may be greater than or equal to less than 0.50.
  • the carbon black of this embodiment preferably has a hydrochloric acid absorption amount of 39 mL/5 g or more.
  • the amount of hydrochloric acid absorbed is the amount of hydrochloric acid that can be retained on the particle surface of carbon black and in the voids formed by the structure and agglomerate (secondary agglomeration of the structure), and is an index for evaluating the degree of development of the structure and agglomerate.
  • the carbon black structure is a structure in which primary particles are connected.
  • the structure of carbon black develops into a complex entangled shape as the primary particles become smaller in size.
  • Carbon black is characterized by its thermal history during synthesis (e.g. thermal history caused by thermal decomposition and combustion reactions of fuel oil, thermal decomposition and combustion reactions of raw materials, rapid cooling with cooling medium and reaction termination, etc.), collision frequency of primary particles.
  • thermal history during synthesis e.g. thermal history caused by thermal decomposition and combustion reactions of fuel oil, thermal decomposition and combustion reactions of raw materials, rapid cooling with cooling medium and reaction termination, etc.
  • collision frequency of primary particles e.g. thermal history caused by thermal decomposition and combustion reactions of fuel oil, thermal decomposition and combustion reactions of raw materials, rapid cooling with cooling medium and reaction termination, etc.
  • the degree of development of structure and agglomerate varies greatly depending on the difference in structure and agglomerate (secondary aggregation of structure).
  • the amount of hydrochloric acid absorbed can be measured according to JIS K1469:2003. Specifically, it is determined by adding hydrochloric acid little by little to 5 g of carbon black in an Erlenmeyer flask, shaking it, and measuring the amount of hydrochloric acid required to form a lump.
  • the amount of hydrochloric acid absorbed may be 39 mL/5 g or more, 40 mL/5 g or more, or 41 mL/5 g or more, from the viewpoint of obtaining the above effects more significantly.
  • the amount of hydrochloric acid absorbed by the carbon black of this embodiment is such that the slurry viscosity described below is 1500 mPa ⁇ s or less.
  • the upper limit of the preferable range of hydrochloric acid absorption amount may be defined by the slurry viscosity described below.
  • the hydrochloric acid absorption amount may be, for example, 49 mL/5 g or less, or 48 mL/5 g or less, from the viewpoint that the slurry viscosity described below is likely to be 1500 mPa ⁇ s or less. That is, in the carbon black of this embodiment, the hydrochloric acid absorption amount is, for example, 39 to 49 mL/5 g, 39 to 48 mL/5 g, 40 to 49 mL/5 g, 40 to 48 mL/5 g, 41 to 49 mL/5 g, or 41 to 48 mL. /5g.
  • the carbon black of this embodiment preferably has a slurry viscosity of 400 mPa ⁇ s or more and 1500 mPa ⁇ s or less.
  • the slurry viscosity refers to the viscosity of a slurry in which 3% by mass of carbon black is dispersed using N-methyl-2-pyrrolidone as a dispersion medium. More specifically, 3% by mass of carbon black and 97% by mass of N-methyl-2-pyrrolidone as a dispersion medium were mixed using a rotation-revolution mixer ("Awatori Rentaro ARV-310" manufactured by Shinky Co., Ltd.). A slurry was obtained by kneading at a rotational speed of 2000 rpm for 30 minutes, and the viscosity of this slurry at 25° C.
  • the viscosity at a shear rate of 10 s -1 is determined by changing the shear rate from 0.01 s -1 to 100 s -1 .
  • the viscosity measured in this manner at 25° C. and a shear rate of 10 s ⁇ 1 is defined as the slurry viscosity.
  • Slurry viscosity is an indicator of the dispersibility and stability of carbon black under shear.
  • carbon black with a slurry viscosity of 400 mPa ⁇ s or more and 1500 mPa ⁇ s or less is used as a carrier for a fuel cell catalyst
  • the catalyst paste which is a mixture of a fuel cell catalyst, an electrolyte, and a solvent, tends to be uniform.
  • the electrode catalyst layer obtained by coating the fuel cell catalyst is difficult to form aggregated particles. Therefore, it becomes easier to obtain better long-term reliability and reaction efficiency.
  • the slurry viscosity may be 450 mPa ⁇ s or more or 500 mPa ⁇ s or more from the viewpoint of obtaining the above effects more significantly.
  • the slurry viscosity may be 1400 mPa ⁇ s or less, or 1300 mPa ⁇ s or less from the viewpoint of obtaining the above effects more significantly. That is, in the carbon black of this embodiment, the slurry viscosity is, for example, 400 to 1500 mPa ⁇ s, 400 to 1400 mPa ⁇ s, 400 to 1300 mPa ⁇ s, 450 to 1500 mPa ⁇ s, 450 to 1400 mPa ⁇ s, 450 to 1300 mPa ⁇ s. , 500 to 1500 mPa ⁇ s, 500 to 1400 mPa ⁇ s or 500 to 1300 mPa ⁇ s.
  • the slurry viscosity of carbon black may be adjusted as appropriate depending on the average primary particle diameter of carbon black, the surface properties of carbon black, the shape of the structure of carbon black, etc.
  • the DBP absorption amount of the carbon black of this embodiment may be, for example, 200 mL/100 g or more, 210 mL/100 g or more, or 220 mL/100 g or more. Further, the DBP absorption amount of the carbon black of this embodiment may be, for example, 400 mL/100 g or less, 390 mL/100 g or less, or 380 mL/100 g or less.
  • the DBP absorption amount of the carbon black of this embodiment is, for example, 200 to 400 mL/100 g, 200 to 390 mL/100 g, 200 to 380 mL/100 g, 210 to 400 mL/100 g, 210 to 390 mL/100 g, 210 to 380 mL/100 g. , 220 to 400 mL/100 g, 220 to 390 mL/100 g, or 220 to 380 mL/100 g.
  • the DBP absorption amount is an index for evaluating the ability to absorb dibutyl phthalate (DBP) in the voids formed by the particle surface and structure of carbon black.
  • DBP absorption amount indicates a value obtained by converting a value measured by the method described in JIS K6221 Method B into a value equivalent to JIS K6217-4:2008 using the following formula (a).
  • DBP absorption amount (A-10.974)/0.7833...(a) [Wherein, A represents the equivalent value of DBP absorption measured by the method described in JIS K6221. ]
  • Carbon black with a developed structure has more necks formed by fusion of primary particles and more voids formed between particles, so the amount of DBP absorbed increases. If the DBP absorption amount is too small, the viscosity of the catalyst paste made by mixing the fuel cell catalyst, electrolyte, and solvent will become too low, making it difficult to apply shearing force due to mixing, and making it difficult to obtain good dispersibility. be. On the other hand, if the amount of DBP absorbed is too large, the viscosity of the catalyst paste may become too high, making it difficult to obtain good dispersibility.
  • the DBP absorption amount is preferably within the above range.
  • the average primary particle size of the carbon black of this embodiment may be, for example, less than 30 nm, less than 29 nm, less than 28 nm, less than 27 nm, less than 26 nm, or less than 25 nm. Further, the average primary particle diameter of the carbon black of this embodiment may be, for example, 10 nm or more. According to the findings of the present inventors, when comparing two types of carbon black that satisfy the above ratio (S 2 /S 1 ) with similar specific surface areas but different average primary particle sizes, it was found that carbon black with a small particle size In the case of carbon black, the particle size of metal particles formed on the carbon black is smaller.
  • carbon black with a large particle size has a high specific surface area due to a porous surface, while carbon black with a small particle size can achieve a high specific surface area even if the surface is relatively smooth. This is thought to be because the number of surfaces in contact increases, and the number of reaction fields for forming metal particles increases.
  • the average primary particle size of carbon black can be determined by measuring the primary particle size of 100 or more carbon black particles randomly selected from a 50,000x magnified image using a transmission electron microscope (TEM) and calculating the average value. can.
  • TEM transmission electron microscope
  • the primary particles of carbon black have a small aspect ratio and a shape close to a true sphere, they are not completely true spheres. Therefore, in this embodiment, the largest line segment connecting two points on the outer periphery of the primary particle in the TEM image is defined as the primary particle diameter of carbon black.
  • the ash content of the carbon black of this embodiment may be, for example, 0.05% by mass or less, 0.03% by mass or less, or 0.02% by mass or less.
  • the ash content can be measured according to JIS K1469:2003, and can be reduced, for example, by classifying carbon black with a device such as a dry cyclone.
  • the sulfur content of the carbon black of this embodiment may be, for example, 50 mass ppm or less.
  • the sulfur content in carbon black exists as acidic functional groups such as sulfuric acid groups on the surface of carbon black.
  • generation of gases such as SOx due to electrochemical reactions inside the battery is suppressed, and deterioration of fuel cell performance due to the gases is significantly suppressed.
  • the sulfur content of carbon black can be calculated by burning carbon black in an oxygen stream, absorbing the generated combustion gas into a hydrogen peroxide solution, and measuring it using ion chromatography.
  • the method for producing carbon black of this embodiment is not particularly limited.
  • raw materials such as hydrocarbons are supplied from a nozzle installed upstream of a reactor, and carbon black is produced by a thermal decomposition reaction and/or a combustion reaction.
  • Carbon black can be obtained by generating black and collecting it from a bag filter directly connected downstream of the reactor.
  • the raw materials used are not particularly limited, and include gaseous hydrocarbons such as acetylene, methane, ethane, propane, ethylene, propylene, butadiene, and oils such as toluene, benzene, xylene, gasoline, kerosene, light oil, and heavy oil. Hydrocarbons can be used. Among them, it is preferable to use acetylene, which has few impurities. Acetylene has a larger heat of decomposition than other raw materials, and the temperature inside the reactor can be raised, so carbon black nucleation dominates particle growth due to addition reactions, reducing the primary particle size of carbon black. be able to.
  • gaseous hydrocarbons such as acetylene, methane, ethane, propane, ethylene, propylene, butadiene, and oils such as toluene, benzene, xylene, gasoline, kerosene, light oil, and heavy oil. Hydrocarbons can be used. Among
  • the present inventors found that it is effective to use multiple raw materials and heat the raw materials before supplying them to the reactor. I discovered that.
  • carbon black produced through the high-temperature section of the reactor and carbon black produced via the low-temperature section coexist, resulting in large variations in properties, but by using multiple raw materials, It is thought that the proportion of polycyclic aromatic hydrocarbons present on the surface of carbon black decreased because the temperature in the reactor became uniform and the reaction history of thermal decomposition and combustion became uniform.
  • heating the raw materials promoted the mixing of multiple raw materials, making it possible to form a more uniform temperature field.
  • the plurality of raw materials are mixed before being supplied to the reactor. When using oily hydrocarbons, it is preferable to gasify them by heating and then supply them.
  • the heating method is not particularly limited, and for example, a tank or transport piping can be heated by heat exchange with a heating medium.
  • oxygen, hydrogen, nitrogen, steam, etc. it is preferable to supply oxygen, hydrogen, nitrogen, steam, etc. to the reactor separately from the raw material serving as the carbon source.
  • gases other than raw materials promote gas agitation in the reactor and increase the frequency of collision and fusion of primary particles of carbon black produced from raw materials.
  • gases other than raw materials carbon black structure develops, and the amount of DBP absorbed tends to increase.
  • oxygen is preferable to use oxygen as the gas other than the raw material. When oxygen is used, part of the raw material is combusted and the temperature inside the reactor increases, making it easier to obtain carbon black with a small particle size and a high specific surface area.
  • a plurality of gases can also be used as the gas other than the raw material.
  • the gas other than the raw material is preferably supplied to the upstream part of the reactor, and is preferably supplied from a different nozzle from that for the raw material.
  • the raw materials supplied from the upstream portion are efficiently stirred, and the structure is facilitated to develop.
  • a cooling medium such as water is sometimes introduced from the downstream part of the reactor to thermally decompose the raw material and stop the combustion reaction, but no effect on structure development has been observed.
  • the fuel cell catalyst of this embodiment has at least one metal particle selected from the group consisting of platinum particles and platinum alloy particles supported on the surface of a fuel cell catalyst carrier (carbon black).
  • the metal particles are strongly supported on the surface of the carrier.
  • the average particle size of the metal particles may be, for example, 2 nm or more. When the average particle size is 2 nm or more, dissolution, corrosion, etc. during potential fluctuations are suppressed.
  • the average particle size of the metal particles may be, for example, 5 nm or less. When the average particle size is 5 nm or less, a sufficient active surface area is ensured, and better fuel cell characteristics are likely to be obtained.
  • the particle size of the metal particles is determined by the length of the longest line segment connecting two points on the outer periphery of the metal particles, as determined by observation with a transmission electron microscope.
  • the average particle size of metal particles can be determined by measuring the particle size of 1000 metal particles and calculating the average value.
  • Platinum particles are particles composed of platinum.
  • Platinum alloy particles are particles composed of an alloy of platinum and other metals (hereinafter referred to as alloy forming metals).
  • alloy forming metals include palladium, rhodium, iridium, ruthenium, iron, titanium, nickel, cobalt, gold, silver, copper, chromium, manganese, molybdenum, tungsten, aluminum, silicon, rhenium, zinc, tin, and the like.
  • platinum-ruthenium alloys are preferred because they are effective in preventing carbon monoxide poisoning.
  • composition of the alloy is not particularly limited, but may be, for example, 30 to 90% by mass of platinum and 10 to 70% by mass of alloy forming metal.
  • the amount of metal particles supported in the fuel cell catalyst may be, for example, 5 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of carbon black.
  • the method for supporting metal particles on carbon black is not particularly limited, and may be, for example, the following method. Carbon black is suspended in water to form a slurry, a metal source is added to this to form a mixed solution A, and sodium borohydride is added in an amount equivalent to 10 times the amount of the metal to form metal particles on the surface of the carbon black. After precipitation, a fuel cell catalyst is obtained by filtering, washing, and drying.
  • platinum sources include hexachloroplatinum aqueous solution, hexahydroxoplatinum aqueous solution, dinitrodiammine platinum aqueous solution, and the like.
  • examples of the alloy-forming metal source include a ruthenium (III) trichloride aqueous solution.
  • a pH adjuster such as an aqueous sodium hydroxide solution may be added as appropriate.
  • the fuel cell catalyst may be subjected to an annealing treatment after supporting metal particles on carbon black, and then used in a fuel cell.
  • the annealing treatment can be performed by heating to 800 to 1000° C., for example, in an inert atmosphere such as argon gas or nitrogen gas, or a reducing atmosphere such as hydrogen gas.
  • the evaluation of the fuel cell catalyst of this embodiment can be performed as follows.
  • a fuel cell catalyst is mixed with a Nafion solution and alcohol is added to form a paste, which is applied to one side of carbon paper and dried to form an electrode catalyst layer (electrode for evaluation).
  • an evaluation electrode was placed on one side of the Nafion membrane (perfluorosulfonic acid electrolyte membrane), and a known electrode was placed on the other side, and thermocompression bonded using a hot press at 130°C. In this way, an electrolyte membrane-electrode assembly (MEA) is obtained.
  • MEA electrolyte membrane-electrode assembly
  • a single cell is completed by sandwiching the MEA between a separator and a current collector plate, and the fuel cell can be evaluated by connecting an electronic load device and a gas supply device. Moreover, the above evaluation can be performed more easily by using a commercially available fuel cell single cell evaluation device.
  • the electrode catalyst layer of this embodiment contains the above fuel cell catalyst and electrolyte.
  • the electrolyte is not particularly limited, and electrolytes used in known fuel cells can be used without particular limitation.
  • perfluorosulfonic acid polymers are preferably used, and examples thereof include Nafion (manufactured by Dupont), Aciplex (manufactured by Asahi Kasei), Flemion (manufactured by Asahi Glass), and the like.
  • the thickness of the electrode catalyst layer may be, for example, 5 ⁇ m or more, or 10 ⁇ m or more. Further, the thickness of the electrode catalyst layer may be, for example, 50 ⁇ m or less, 40 ⁇ m or less, or 30 ⁇ m or less. That is, the thickness of the electrode catalyst layer may be, for example, 5 to 50 ⁇ m, 5 to 40 ⁇ m, 5 to 30 ⁇ m, 10 to 50 ⁇ m, 10 to 40 ⁇ m, or 10 to 30 ⁇ m.
  • the fuel cell of this embodiment includes the electrode catalyst layer of this embodiment described above.
  • the structure other than the electrode catalyst layer is not particularly limited, and may be the same structure as a known fuel cell.
  • the fuel cell of this embodiment may include, for example, a first separator, an anode electrode catalyst layer, an electrolyte membrane, a cathode electrode catalyst layer, and a second separator. It may include a separator, a first gas diffusion layer, an anode electrode catalyst layer, an electrolyte membrane, a cathode electrode catalyst layer, a second gas diffusion layer, and a second separator.
  • one of the anode electrode catalyst layer and the cathode electrode catalyst layer may be the electrode catalyst layer of this embodiment described above.
  • the first separator and the second separator may be any separator provided with a gas flow path.
  • the first separator and the second separator may be separators used in known fuel cells.
  • the first separator and the second separator may be made of, for example, stainless steel, aluminum alloy, carbon, or the like.
  • the first gas diffusion layer and the second gas diffusion layer may be gas diffusion layers used in known fuel cells.
  • the first gas diffusion layer and the second gas diffusion layer are, for example, a coating layer (for example, a coating made of a carbon material and a water repellent material) on the surface of a base material (for example, carbon fiber paper, woven fabric, nonwoven fabric, etc.). layer) may be provided.
  • One of the anode electrode catalyst layer and the cathode electrode catalyst layer may be the electrode catalyst layer of the above-described present embodiment, and the other may be another electrode catalyst layer. Moreover, both the anode electrode catalyst layer and the cathode electrode catalyst layer may be the electrode catalyst layers of the above-described present embodiment. Electrode catalyst layers other than the electrode catalyst layer of this embodiment may be electrode catalyst layers used in known fuel cells.
  • the electrolyte membrane may be an electrolyte membrane used in known fuel cells.
  • a perfluorosulfonic acid polymer is preferably used for the electrolyte membrane, and may be, for example, Nafion (manufactured by Dupont), Aciplex (manufactured by Asahi Kasei), Flemion (manufactured by Asahi Glass), or the like.
  • Example 1 Manufacture of carbon black> From a nozzle installed at the upstream part of a carbon black reactor (furnace length: 6 m, furnace diameter: 0.65 m), acetylene as a raw material is fed at a rate of 12 Nm 3 /h, toluene at a rate of 32 kg/h, and oxygen as a gas other than the raw material at a rate of 21 Nm 3 /h . h to produce carbon black, which was collected by a bag filter installed downstream of the reactor. Thereafter, it was passed through a dry cyclone device and a magnet for iron removal and collected into a tank. Note that acetylene, toluene, and oxygen were heated to 115° C. and then supplied to the reactor. The following physical properties of the obtained carbon black were measured. The evaluation results are shown in Tables 1 and 2.
  • FIG. 1 is a diagram showing a chart of m/z 57 and m/z 128 detected by temperature-programmed desorption gas analysis of the carbon black of Example 1.
  • the obtained absorption liquid was introduced into an ion chromatography analyzer, the peak area of sulfate ions was measured, and the sulfur content in the sample was calculated based on a calibration curve prepared in advance from a sulfate ion standard solution.
  • Platinum particles were supported on carbon black using the following method.
  • a platinum solution prepare 1000 g (platinum content: 46 g) of a dinitrodiammine platinum nitric acid solution with a platinum concentration of 4.6% by mass. 46 g of carbon black is immersed in this platinum solution, and after stirring, 100% ethanol is added as a reducing agent. 100 mL of was added. Next, the mixture was stirred and mixed under heating and reflux for 7 hours, so that the platinum particles were supported on the carbon black. Filtration and drying were performed to obtain a fuel cell catalyst having a supported amount of platinum particles of 50 parts by mass based on 100 parts by mass of carbon black.
  • the particle size of 1000 platinum particles was measured by TEM observation (magnification: 100,000 times), and the average value was determined.
  • the evaluation results are shown in Table 2.
  • the obtained fuel cell catalyst was annealed by holding it at 900° C. for 1 hour in 100% hydrogen gas.
  • Electrode catalyst layer To 0.05 g of a fuel cell catalyst, 0.1 g of a 5% by mass Nafion solution (Nafion 1100EW, manufactured by Sigma-Aldrich) and 0.6 g of 2-propanol were added and mixed to form a catalyst paste. Next, a catalyst paste was applied to carbon paper so that the platinum content was 0.3 mg/cm 2 and dried at room temperature to obtain an electrode catalyst layer. The surface of the obtained electrode catalyst layer was observed using a SEM (magnification: 1000 times), and the number of aggregated particles of 10 ⁇ m or more existing in an area of 100 ⁇ m in length ⁇ 100 ⁇ m in width was determined. Here, the size of the aggregated particles was determined from the diameter of the smallest circle that could surround each aggregated particle. The results are shown in Table 3.
  • a fuel cell was manufactured using the electrode catalyst layer obtained above as a cathode electrode.
  • an anode electrode was produced in the same manner as ⁇ Manufacture of electrode catalyst layer> above, except that the fuel cell catalyst was changed to "TEC10E50E" (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.).
  • the Nafion membrane, the cathode electrode, and the anode electrode were overlapped so that the cathode electrode and the anode electrode faced each other with the Nafion membrane in between, and pressed at 130° C. and 9.8 MPa for 3 minutes to obtain an MEA.
  • a separator, a gasket, and an end plate were stacked on the upper and lower surfaces of the MEA in this order, and fixed with four screws to produce a fuel cell.
  • Example 2 and 3 Carbon black was produced in the same manner as in Example 1, except that the amount of oxygen supplied in ⁇ Production of carbon black> was changed to 22 Nm 3 /h (Example 2) or 24 Nm 3 /h (Example 3). and evaluated. The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 4 In ⁇ Production of carbon black>, carbon black was produced and evaluated in the same manner as in Example 1, except that the temperature during supply of toluene was changed to 100°C. The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 5 In ⁇ Manufacture of carbon black>, carbon black was produced and evaluated in the same manner as in Example 1, except that the temperature during acetylene supply was changed to 85 ° C., and the temperature during toluene supply was changed to 100 ° C. . The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 6 In ⁇ Production of carbon black>, carbon black was produced and evaluated in the same manner as in Example 1, except that the temperature during acetylene supply was changed to 85 ° C., and the temperature during toluene supply was changed to 85 ° C. . The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 7 Carbon black was produced and evaluated in the same manner as in Example 1, except that the acetylene supply rate was changed to 13 Nm 3 /h, the toluene supply rate was changed to 35 kg/h, and the oxygen supply rate was changed to 26 Nm 3 /h. did. The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 8 Carbon black was produced and evaluated in the same manner as in Example 1, except that 32 kg/h of benzene was heated to 115° C. and supplied instead of toluene. The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 1 Carbon black was produced and evaluated in the same manner as in Example 1, except that the amount of oxygen supplied was changed to 20 Nm 3 /h. The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Carbon black was prepared and evaluated in the same manner as in Example 1, except that the acetylene supply rate was changed to 11 Nm 3 /h, the toluene supply rate was changed to 30 kg/h, and the oxygen supply rate was changed to 24 Nm 3 /h. .
  • the results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 9 The carbon black obtained in Comparative Example 1 was oxidized in an electric furnace heated to 720° C. to obtain carbon black. The obtained carbon black was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 10 Carbon black was produced and evaluated in the same manner as in Example 1, except that the classification conditions of the dry cyclone device were changed to adjust the ash content. The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 11 Carbon black was produced and evaluated in the same manner as in Example 1, except that the iron content was adjusted by changing the magnetic flux density conditions of the iron removal magnet. The results are shown in Tables 1 and 2. Further, using the obtained carbon black, a fuel cell catalyst, an electrode catalyst layer, and a fuel cell were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • the carbon black of the example as a carrier for the fuel cell catalyst, agglomeration in the electrode catalyst layer was suppressed and a high-performance fuel cell was obtained. It was confirmed that the catalyst is capable of achieving both high dispersibility and high reaction efficiency.
  • the fuel cell catalyst carrier of the present invention can be suitably used to realize a fuel cell catalyst that can achieve both high dispersibility and high reaction efficiency. Further, the fuel cell catalyst of the present invention can achieve both high dispersibility and high reaction efficiency, and can be suitably used as a fuel cell catalyst.

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Abstract

La présente invention concerne un support de catalyseur pour piles à combustible, le support de catalyseur étant formé de noir de carbone, la surface spécifique étant de 170 m2/g à 400 m2/g ; et le rapport (S2/S1) entre la zone de pic (S2) du pic m/z 128 et la zone de pic (S1) du pic m/z 57 tel que déterminé par analyse de gaz de désorption à température programmée étant inférieur à 2,00.
PCT/JP2023/012971 2022-05-13 2023-03-29 Support de catalyseur pour piles à combustible, catalyseur pour piles à combustible, couche de catalyseur d'électrode et pile à combustible WO2023218790A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006252938A (ja) * 2005-03-10 2006-09-21 Gs Yuasa Corporation:Kk 固体高分子形燃料電池用電極およびその製造方法
WO2015045083A1 (fr) * 2013-09-27 2015-04-02 株式会社日立製作所 Catalyseur d'électrode de pile à combustible et ensemble membrane/électrode l'utilisant
WO2019017252A1 (fr) * 2017-07-18 2019-01-24 住友電気工業株式会社 Corps métallique poreux et collecteur de courant pour batterie au nickel-métal-hydrure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006252938A (ja) * 2005-03-10 2006-09-21 Gs Yuasa Corporation:Kk 固体高分子形燃料電池用電極およびその製造方法
WO2015045083A1 (fr) * 2013-09-27 2015-04-02 株式会社日立製作所 Catalyseur d'électrode de pile à combustible et ensemble membrane/électrode l'utilisant
WO2019017252A1 (fr) * 2017-07-18 2019-01-24 住友電気工業株式会社 Corps métallique poreux et collecteur de courant pour batterie au nickel-métal-hydrure

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