WO2017086250A1 - Matériau d'électrode pour pile à combustible, et son procédé de préparation - Google Patents

Matériau d'électrode pour pile à combustible, et son procédé de préparation Download PDF

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Publication number
WO2017086250A1
WO2017086250A1 PCT/JP2016/083547 JP2016083547W WO2017086250A1 WO 2017086250 A1 WO2017086250 A1 WO 2017086250A1 JP 2016083547 W JP2016083547 W JP 2016083547W WO 2017086250 A1 WO2017086250 A1 WO 2017086250A1
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fuel cell
molded body
metal
electrode material
electrode
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PCT/JP2016/083547
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English (en)
Japanese (ja)
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鈴木健治
田邊重之
麻生忍
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株式会社健明
ポーライト株式会社
鈴木健治
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Publication of WO2017086250A1 publication Critical patent/WO2017086250A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a fuel cell electrode material used as an air electrode catalyst layer or a fuel electrode catalyst layer, and a method for producing the same.
  • polymer electrolyte fuel cells have attracted attention, research and development as one of the clean energy sources that do not generate carbon dioxide. In addition, it is used as a stationary electric and heat combined device, and is also being developed as a power source for driving vehicles such as electric vehicles.
  • a catalyst in which a noble metal such as platinum or a platinum alloy is supported on carbon black is used as a cathode catalyst and an anode catalyst in order to activate a reaction process in an electrode.
  • platinum is a very expensive material because it is a scarce resource and the amount of mining is limited. Therefore, development and commercialization of fuel cells that do not use platinum or other platinum group elements are desired.
  • fuel cell catalyst fine particles such as Pt are supported on the surface of fullerenes, and fullerenes are used as a core, and the surface is a core-shell catalyst covered with fuel cell catalyst fine particles such as Pt. It is known that a catalytic action of hydrogen oxidation or oxygen reduction is exhibited on the surface (see, for example, Patent Document 1).
  • FIG. 8 shows an example of a configuration (cross-sectional view) of a conventional polymer electrolyte fuel cell 100.
  • a fuel electrode 200 and an air electrode 300 are provided on both sides of the PEM membrane 4.
  • the PEM film 4 is electrically insulated and blocks the movement of hydrogen gas (H 2 ), oxygen gas (O 2 ), water vapor (H 2 O), etc. existing on both sides to the other side.
  • platinum carbon black carrying fine platinum (Pt) on the surface on the PEM film 4 side.
  • This platinum promotes a reaction in which a hydrogen molecule (H 2 ) releases an electron (e ⁇ ) and a reaction in which an oxygen molecule (O 2 ) is bonded to a hydrogen ion (H + ) and an electron (e ⁇ ).
  • Acts as a catalyst in particular, in low-temperature type fuel cells (for example, in the range of about 20 to 200 ° C.), the use of platinum in this way is an essential technology. Therefore, as described above, the solid polymer fuel cell 100 and the like are used. The challenge was how to use less platinum. What should be desired is the development and practical application of electrode materials for fuel cells that do not use platinum or other platinum group elements.
  • the disclosed technology such as the above-mentioned patent document relates to a method for increasing the catalytic activity with a smaller amount of platinum, and a technology for increasing the catalyst performance with the same amount used, and as a low-temperature fuel cell, It is not a technology for fuel cells that do not use platinum group elements. Further, it does not disclose a technique for a fuel cell that does not use a platinum group element.
  • the present inventors have invented a fuel electrode material that does not use a platinum group element, and filed it as Japanese Patent Application No. 2015-124297.
  • the invention described in Japanese Patent Application No. 2015-124297 has Ni as a main component. Although Ni is considerably cheaper than the platinum group element, it is a rare metal and an expensive metal.
  • the problem to be solved by the present invention is to provide an electrode material for a fuel cell that is used as an air electrode catalyst layer or a fuel electrode catalyst layer that does not use a platinum group element as a low-temperature fuel cell, and a method for producing the same. That is.
  • Another object of the present invention is to provide an electrode material for a fuel cell that is used as an air electrode catalyst layer or a fuel electrode catalyst layer that does not use Ni or uses a small amount of Ni, and a method for producing the same.
  • an electrode material for a fuel cell is an electrode material for a fuel cell used as an air electrode catalyst layer or a fuel electrode catalyst layer, and includes Ru, Rh, Pd, Os, Ir, and Pt. It is an electrode material for a fuel cell that does not contain a platinum group element.
  • the fuel cell electrode material is a molded body mainly composed of Fe, and includes a molded body containing at least a plurality of different transition metals belonging to Fe and 3d transition metal as a metal material.
  • the main feature is that it is made of a mixture containing each powder of the metal material and has voids dispersed in the molded body so that the fuel used in the fuel cell can permeate the molded body.
  • the plurality of different transition metals include at least one of Ni, Mn, Cr, and Ti, and the molded body includes a transition metal other than the included transition metal.
  • the metal material mainly includes any one of Cu, Zn, Al, or Mg, which has a higher electrical conductivity than the transition metal contained therein.
  • the fuel cell electrode material according to the present invention is characterized in that the plurality of different transition metals include at least Ni or Cu.
  • the composition ratio of the metal material in the molded body is 1 to 3 mass% of Mg or Zn when the mass of the molded body is 100 mass%.
  • the electrode material for a fuel cell according to the present invention is mainly characterized in that the porosity of the molded body is in a range of 20% to 40% with respect to the volume of the molded body.
  • the powder is spherical or needle-shaped, or at least one type of the metal material is spherical and the other type of the metal material is needle-shaped.
  • the main feature is that it has been processed.
  • the fuel cell electrode material according to the present invention is mainly characterized in that the molded body carries a light emitting substance that emits light by infrared rays or ultraviolet rays.
  • a method for producing a fuel cell electrode material according to the present invention is a method for producing a fuel cell electrode material for producing the fuel cell electrode material.
  • the manufacturing method includes a pulverization step of pulverizing the metal material used for the molded body to 200 ⁇ m or less as a powder, a mixing step of mixing the powder so as to be uniformly dispersed after the pulverization step, After the mixing step, the uniformly dispersed powder is pressed at a pressure of 500 to 800 Mpa to form a compact, and after the pressurizing step, the sintering step is performed to sinter the compact.
  • the main feature is to include.
  • the sintering temperature is higher than the melting point of the metal having the highest electrical conductivity among the metal materials, and the most electrically conductive material.
  • the main feature is that it is in a range lower than the melting point of a metal other than a high-rate metal.
  • the fuel cell electrode material manufacturing method according to the present invention is mainly characterized in that it further includes a luminescent substance supporting step of supporting a luminescent substance that emits light by infrared rays or ultraviolet rays on the molded body.
  • the electrode material for a fuel cell according to the present invention can be used as a catalyst that does not use a platinum group element, the manufacturing cost of a low-temperature fuel cell can be reduced. In addition, since a metal that is not a scarce resource can be used, the problem of resource problems can be solved.
  • the method for manufacturing a fuel cell electrode material according to the present invention reduces the manufacturing cost of a low-temperature fuel cell by using an electrode material for a fuel cell that is used as an air electrode catalyst layer or a fuel electrode catalyst layer that does not use a platinum group element. can do.
  • a metal that is not a scarce resource can be used, the problem of resource problems can be solved.
  • the figure which shows an example of a structure of the fuel cell of embodiment which concerns on this invention Diagram showing an example of the structure of the fuel electrode
  • Diagram showing experimental data of fuel cell using prototype fuel cell electrode material The figure which shows an example of a structure of the conventional polymer electrolyte fuel cell
  • FIG. 1 shows an example of the configuration of a fuel cell 1 according to an embodiment of the present invention.
  • the fuel cell 1 shown in FIG. 1 is an example of a polymer electrolyte fuel cell. As shown in FIG. 1, the fuel cell 1 includes a fuel electrode 2, an air electrode 3, a PEM membrane 4, a hydrogen gas inlet 5, an oxygen gas inlet 6, a hydrogen gas supply connection 11, an oxygen gas supply connection 12, and A water discharge unit 13 is provided.
  • the fuel electrode 2 is an anode electrode having a fuel cell electrode material 21 used as a fuel electrode catalyst layer that does not contain a platinum group element (Ru, Rh, Pd, Os, Ir, Pt).
  • Hydrogen is supplied to the fuel electrode 2 through, for example, a hydrogen gas supply connection portion 11 connected to an external hydrogen supply source, and a hydrogen gas inlet portion 5 that takes in hydrogen gas supplied from the hydrogen supply source into the fuel cell 1.
  • Gas (H 2 ) is supplied.
  • fuel such as methanol (CH 3 OH) may be supplied instead of hydrogen gas.
  • the supplied hydrogen gas fuel is decomposed into hydrogen ions (H + ) and electrons (e ⁇ ) by a reaction of H 2 ⁇ 2H + + 2e ⁇ . Thereafter, hydrogen ions pass through the inside of the PEM film 4, and electrons move to the air electrode 3 through the electrode connection terminals 14 and the load 15.
  • a PEM (Proton Exchange Membrane) film 4 is provided with a structure sandwiched between a fuel electrode 2 and an air electrode 3.
  • the PEM membrane 4 is an electrolytic membrane that can carry hydrogen ions (H + ) that can be ionized by hydrogen gas from the fuel electrode 2 side to the air electrode 3 side.
  • the air electrode 3 is a cathode electrode having a fuel cell electrode material 31 used as an air electrode catalyst layer not containing a platinum group element.
  • an oxygen gas supply connection unit 12 connected to an external oxygen supply source and an oxygen gas suction port 6 for taking oxygen gas supplied from the oxygen supply source into the fuel cell 1 are connected to the air electrode 3. Gas (O 2 ) is supplied.
  • FIG. 2 shows an example of the structure of the fuel electrode 2a (another embodiment of the fuel electrode 2).
  • FIG. 2A is a cross-sectional view
  • FIG. 2B is a plan view.
  • FIG. 3 shows a configuration of a fuel cell 1a (another embodiment of the fuel cell 1) having the fuel electrode 2a and the air electrode 3a of FIG.
  • the fuel electrode 2a is composed of a fuel cell electrode material 21 and a conductive material 22, as shown in FIG.
  • the conductive material 22 is a well-known metal material that can conduct (conductive).
  • the conductive material 22 is provided with a plurality of holes 23 penetrating from one flat surface to the other surface. Thereby, for example, the hydrogen gas taken into the hydrogen gas inlet 5 shown in FIG. 3 can reach the fuel cell electrode material 21 through the plurality of holes 23 of the conductive material 22.
  • the conductive material 22 can be connected to the electrode connection terminal 14 and is arranged and connected so as to be conductive with the fuel electrode 2a.
  • the air electrode 3a shown in FIG. 3 has the same structure as that of the fuel electrode 2a shown in FIG. 2, and is composed of a fuel cell electrode material 31 and a conductive material 32.
  • an object of the present invention is to provide a fuel cell electrode material having a highly active catalytic action using different transition metals other than platinum group elements or a combination of these with other metals.
  • the fuel cell electrode materials 21 and 31 are made of a metal material containing no platinum group elements (Ru, Rh, Pd, Os, Ir, Pt).
  • the fuel cell electrode materials 21 and 31 are formed bodies containing Fe as a main component and containing at least Fe and a plurality of different transition metals belonging to the 3d transition metal as metal materials.
  • This molded body is made of a mixture containing powders of these metal materials, and has voids dispersed in the molded body so that the fuel used in the fuel cell 1a can permeate the molded body.
  • the plurality of different transition metals include at least one of Ni, Mn, Cr, and Ti belonging to the 3d transition element.
  • the molded body contains any one of Cu, Zn, Al, or Mg, which is higher in electrical conductivity than the transition metal contained, as a metal material other than the contained transition metal.
  • FIG. 4 shows the appearance of the prototype fuel cell electrode materials 21 and 31 (prototypes).
  • ⁇ Fuel cell electrode material> In the examples of the fuel cell electrode materials 21 and 31 of the present embodiment, for example, molded bodies containing a plurality of different transition metals described below are used.
  • the embodiment shown in FIG. 4 contains a large amount of Fe as the 3d transition metal among the different transition metals, and as the other 3d transition metal, a small amount of Cu in the mass ratio of Fe and about the same amount as Fe.
  • a molded body containing a small amount of Ni That is, more preferably, from the viewpoint of material cost, it is a molded body mainly composed of Fe among 3d transition metals.
  • the molded body thus produced has a large number of holes on the surface of the molded body so that hydrogen gas, oxygen gas, or a solution serving as a fuel can pass through the thickness direction of the molded body, and It has a structure (also referred to as a multiporous structure) in which many voids are provided inside the molded body.
  • the gap between the powders decreases as the pressure increases.
  • the porosity of a molded object can be adjusted with the magnitude
  • the porosity changes slightly depending on the sintering temperature and time during sintering after pressurization, so that the molded product that is finally produced can be obtained by adjusting and controlling these conditions as well. Manufactured to be in the range of porosity.
  • the void provided in the molded body is a space surrounded by the surfaces of a plurality of different transition metals or other metals. In addition, on the surface, a plurality of holes that continue to the voids of the molded body are formed. As the plurality of transition metals contained in the molded body, 3d transition metals are preferable.
  • a plurality of different 3d transition metals contain, for example, mainly Ni and a small amount of Cu and Fe.
  • the composition ratio of Fe, Ni, and Cu is 1: 48: 4 in terms of mass ratio.
  • a plurality of different 3d transition metals contain, for example, Fe as a main component, Ni in the same amount or a small amount, and Cu or the like in a small amount.
  • the composition ratio of Fe, Ni, and Cu is 48: 48: 4 in terms of mass ratio.
  • the hydrogen ions (H + ) that have reached the air electrode 3a are connected to an oxygen gas (O 2 ), an external load 15 and the like in the vicinity of the boundary where the PEM membrane 4 and the fuel cell electrode material 31 are in contact with each other.
  • Water (H 2 O) is generated by a chemical reaction with electrons (e ⁇ ) supplied from the terminal 14 as shown in (Formula 2).
  • (Air electrode) 1 / 2.O 2 + 2H + + 2e ⁇ ⁇ H 2 O (Formula 2)
  • a catalytic action that promotes the reaction between oxygen molecules, hydrogen ions, and electrons is exerted on the surface of the void in the electrode material 31 for the fuel cell and the surface near the boundary with the PEM film 4.
  • a catalyst material for a low-temperature fuel cell a material in which a platinum catalyst is supported on a carbon black carrier has been used. Instead, a fuel cell electrode material 31 can be used.
  • FIG. 4 shows an external appearance of the prototype.
  • FIG. 6 is a list showing an outline of the prototypes (fuel cell electrode materials 21 and 31) that have been experimentally produced.
  • the fuel cell electrode materials 21 and 31 for use in the fuel cell 1a are the fuel cell electrode materials 21 and 31 for use in the fuel cell 1a.
  • the fuel cell electrode materials 21 and 31 shown in FIG. 4 have a large number of holes in a disk-shaped surface. Many of the holes are formed by connecting many of the voids inside the molded body. Further, the void inside the molded body is formed so that the fuel used in the fuel cell 1a can pass through the molded body. For example, when a water droplet is dropped on the fuel cell electrode materials 21 and 31 shown in FIG. 4 and the surface is rubbed by hand with the surface immersed in the water droplet, the water droplet is absorbed into the molded body.
  • prototypes No11, No12, No13, and No14 shown in FIG. 6 were prototyped for use in the fuel cell electrode materials 21 and 31 of the fuel cell 1a.
  • the respective materials, sintering temperature, sintering time, pressure during sintering, and other conditions are as shown below.
  • the metal materials of prototype No. 11 and No. 12 are 48Fe-48Ni-4Cu. That is, the metal material contains Fe (iron), Ni (nickel), and Cu (copper) metals in a mass ratio of about 48: 48: 4. Further, the metal material of trial production No13 and No14 is Fe-48Ni-4Cu. That is, the metal material contains Fe (iron), Ni (nickel), and Cu (copper) metals in a mass ratio of approximately 1: 48: 4.
  • the powder to be mixed for manufacturing the molded body is spherical or acicular, or at least one type of metal material is processed into a spherical shape and another type of metal material is processed into an acicular shape.
  • At least the metal having the lowest melting point is spherical, and the other metal having the highest melting point is a needle-like powder.
  • the mixed powder when the mixed powder is pressure-molded, it is easy to form a void having good permeability in the finished molded body. Further, if the metal having the lowest melting point is a spherical powder, the surface area when joining to another metal can be increased.
  • Each transition metal or metal, or an alloy containing the transition metal or the like is pulverized by a pulverizer so as to be equal to or smaller than a predetermined average particle diameter to obtain powder.
  • the average particle diameter of the powder (for example, the length of the longitudinal portion of the longitudinal shape or the outer diameter of the sphere) is 200 ( ⁇ m) or less.
  • the pulverized powder is passed through a mesh that allows a pore diameter of about 200 ( ⁇ m) or less to pass through, for example, in a processing step, and sieved. This is because if the average particle diameter exceeds 200 ( ⁇ m), the strength becomes difficult due to warpage or cracks of the molded article to be produced.
  • the average particle size is 10 to 200 ( ⁇ m).
  • the average particle diameter of many powders is less than 10 ( ⁇ m)
  • voids (pores) are likely to close during pressing and sintering, and the manufactured compact has a permeability of oxygen, hydrogen, etc. It is because it falls.
  • the average particle diameter may be less than 10 ( ⁇ m) in a small part of the powder by treatment with a pulverizer or the like, but there is no practical problem when a very small amount is contained.
  • Each transition metal or metal powder is mixed so as to be uniformly dispersed by a mixer or the like, and the mixed powder is put into a mold for molding and pressed at a predetermined pressure.
  • the pressure at the time of pressurization is about 5 to 8 (t / cm 2 ), in other words, about 500 to 800 (Mpa).
  • the voids also referred to as pores
  • the voids are in the above-described range and have voids as much as possible because they affect the transmittance of the fuel electrode 2 through which hydrogen passes and the air electrode 3 through which oxygen passes. A higher rate is preferred.
  • Sintering temperature 1100-1400 ° C As a guideline, when the sintering temperature is below 1100 ° C., the melting point of Cu contained in the molded body is 1084 ° C., particularly on the inner side of the molded body. In this case, since Cu having high electrical conductivity does not melt, it is difficult to closely bond to other transition metal powders. On the other hand, when the sintering temperature exceeds 1400 ° C., especially when the melting point of Ni contained in the compact is higher than 1455 ° C., a certain amount of voids are provided in the pressure-molded state. Since melting of Ni starts by heating, the formed voids are extremely deformed, and problems such as blocking pores occur. Moreover, it becomes difficult to adjust a desired porosity.
  • the method for manufacturing the fuel cell electrode materials 21 and 31 includes the following steps.
  • a 1st process is a grinding
  • the pulverizing step further includes a shape processing step in which the powder is processed into a spherical shape or a needle shape, or at least one type of metal material is processed into a spherical shape and another type of metal material is processed into a needle shape.
  • the second step is a mixing step in which powders containing different transition metals are mixed so as to be uniformly dispersed after the pulverization step.
  • the third step is a pressurizing step in which the uniformly dispersed powder is put into a mold after the mixing step and is pressed at a pressure of about 500 to 800 MPa to form a molded body.
  • a 4th process is a sintering process which sinters a molded object at high temperature after a pressurization process.
  • the sintering time is about 4 to 6 hours at the sintering temperature set in the sintering process.
  • the sintering temperature is in a range higher than the melting point of the metal having the highest electrical conductivity among the metal materials and lower than the melting point of the metal other than the metal having the highest electrical conductivity.
  • the reason for the above sintering temperature is that when heating is started in the sintering process, the powders are joined by surface diffusion, and the heating temperature is the melting point of the metal having the highest electrical conductivity among the included metals. As a result, the internal diffusion also occurs inside the powder of the molded body, and the powders are bonded to each other. As a result, a metal having high electrical conductivity is closely bonded to other powders in the sintered compact.
  • 48Fe-48Ni-4Cu or Fe-48Ni-4Cu molded body metal material includes Fe and Ni belonging to the 3d transition element, and further includes the 3d transition metal Fe, Ni contained as the metal material.
  • a case of an example including Cu having a higher electric conductivity will be described.
  • Cu is also a 3d transition metal.
  • the melting point of Cu is 1084 ° C.
  • the melting point of Fe is 1536 ° C.
  • the melting point of Ni is 1455 ° C. (see Science Chronology, Vol. 88, 2015).
  • Fe 8.9 (10 -8 ⁇ m)
  • Al 2.50 (10 ⁇ 8 ⁇ m)
  • Cu 1.55 (10 ⁇ 8 ⁇ m
  • the sintering temperature is the melting point of the metal Cu having the highest electrical conductivity among the metal materials.
  • the range is higher than 1084 ° C. and lower than the melting point of the metal other than the metal having the highest electrical conductivity (Ni melting point: 1455 ° C.). That is, the sintering temperature is set in the range of 1100 to 1400 ° C., for example.
  • FIG. 5A shows a state in which the prototype fuel cell is disassembled for each component material
  • the prototype fuel cell shown in FIG. 5A is a prototype based on the configuration of the fuel cell 1a of the present embodiment shown in FIG. Specifically, the fuel cell 1a using each of the prototype No. 11, No. 12, No. 13, and No. 14 shown in FIG. 6 as the fuel cell electrode materials 21 and 31 shown in FIG. 3 is made into four types of prototype fuel cells. It is.
  • the fuel cell electrode materials 21 and 31 shown in FIG. 5A are calculated on the basis of a substantially disk-shaped average outer shape in each of the prototypes No. 11, No. 12, No. 13, and No. 14 shown in FIG. It is about 8.4 to 8.9 (cm 2 ).
  • the experimental comparison fuel cell shown in FIG. 5B is based on the configuration of the fuel cell 100 of the present embodiment shown in FIG. Specifically, a commercially available structure using the electrode catalysts 201 and 301 (referred to as a comparative sample (B)) in which platinum is supported on a carbon carrier on the fuel electrode 200a and the air electrode 300a shown in FIG. 5B. This is a fuel cell.
  • FIG. 6 is a list showing an outline of these prototypes. In particular, it shows characteristics such as the external shape and density of the prototype.
  • FIG. 6 for each prototype No. (prototype type) of the molded body used as the fuel cell electrode materials 21 and 31, the electrode material, the substantially disk-shaped average outer shape, the average thickness, the density, the relative density, and the sintering temperature are shown. Show.
  • the production conditions of the prototypes No. 11 to No. 14 are as described above for the sintering temperature, sintering time, sintering conditions such as pressure during sintering, and other conditions.
  • the prototype No. 11 is mainly used.
  • No12, No13, No14 will be described with respect to the differences in the trial production conditions.
  • the metal materials of trial production No11 and No12 are 48Fe-48Ni-4Cu, and the metal material of trial production No13 and No14 is Fe-48Ni-4Cu.
  • the notation of 48Fe-48Ni-4Cu indicates that the composition ratio of Fe (iron), Ni (nickel), Cu (copper) contained as a metal material is 48: 48: 4 in mass ratio, and Fe-48Ni
  • the notation of -4Cu indicates that the mass ratio is 1: 48: 4. In this material, each metal is easily available, and the material cost is low.
  • the relative density of the molded body shown in FIG. 6 is calculated as follows. In the known technology, if the particle diameter of the close-packed particles is combined (the smaller particles are filled in the gaps between the particles and the particles are mixed and adjusted), the theoretical porosity can be filled to about 4%. Are known. Therefore, the relative density of the molded body is calculated by setting such a metal plate that is closest packed (filled with 96% of particles) to 100% relative density.
  • Fe-48Ni-4Cu and 48Fe-48Ni-4Cu at a relative density of 100% is calculated using the following data (see Science Chronology, Vol. 88, 2015) did.
  • the sintering temperature of the trial No. 11 is the above temperature Hi, and is in the range of the center temperature 1200 ° C. sufficiently higher than the melting point 1084 ° C. of Cu.
  • the sintering temperature of the trial No. 12 is the temperature Lo, which is about 1100 ° C. at the center temperature close to the melting point of Cu of 1084 ° C.
  • the sintering temperature of the prototypes No. 13 and No. 14 is the temperature Lo.
  • the Cu solid powder changes to the liquid state. That is, in the sintering process, which is the sintering temperature of the prototype No. 11, if Cu has a lower melting point than other transition metals and the sintering temperature is 1100 to 1300 ° C., Cu having high conductivity (high electrical conductivity) is obtained. Melts and is in a state of being closely bonded to Ni and Fe powder having a high melting point (melting point higher than that of one metal).
  • the sintering temperature of the prototypes Nos. 12, 13, and 14 has a center temperature of 1100 ° C., and in particular, many portions on the inner side of the molded body have 1000 to 1084 sintering temperatures lower than the melting point of Cu of 1084 ° C. It is considered to be in the range of ° C., and in the sintering process, since it remains a Cu solid powder at the time of pressure forming, it is not in a state where it is sufficiently bonded to Ni and Fe powder. Conceivable.
  • FIG. 7 is a diagram showing experimental data of a fuel cell using a prototype fuel cell electrode material.
  • the experimental results shown in FIG. 7 show that in the configuration of FIG. 3, a voltage tester was connected to the electrode connection terminal 14 instead of the load 15, and the interelectrode voltage of the prototype fuel cell (corresponding to the fuel cell 1a) was measured. Data is shown. Further, in the configuration of FIG. 8, similarly, data obtained by measuring the interelectrode voltage of the experimental comparison fuel cell (corresponding to the fuel cell 100) is shown. Note that the ambient temperature during measurement is about room temperature.
  • the horizontal axis indicates the measurement time (minutes), and the vertical axis indicates the voltage between electrodes (mV).
  • the interelectrode voltage is a voltage between the electrode connection terminals 14 shown in FIG. Further, since the voltage tester has a high resistance, a slight current flows during measurement of the prototype fuel cell and the experimental fuel cell.
  • the terminal voltage of the experimental comparative fuel cell was measured around 500 to 630 (mV).
  • the terminal voltage of the experimental fuel cell was an average voltage of about 100 to 300 (mV) lower than that of the comparative sample (B) using platinum as a catalyst.
  • the terminal voltage of the prototype fuel cell was a voltage lower by about 300 to 400 (mV).
  • the terminal voltage of the prototype fuel cell is a low voltage of about 280 to 380 (mV)
  • the terminal voltage of the prototype fuel cell is a voltage as low as about 100 to 300 (mV).
  • the terminal voltage of the experimental comparison fuel cell was 500 to 630 (mV), but the same material configuration as that of this experimental comparison fuel cell (however, the PEM membrane 4 before this experiment was used).
  • the terminal voltage of the experimental comparison fuel cell was 1.2 (V) in the measurement under the same conditions). For this reason, in this experiment after replacing the PEM membrane 4, there is a common factor (mainly after the replacement) that the terminal voltage is not sufficiently generated (at the open circuit voltage) in the experimental comparison fuel cell and the prototype fuel cell for some reason. It is considered that there was an influence of the PEM film 4).
  • the same PEM membrane 4 is used for the experimental comparison fuel cell and the prototype fuel cell.
  • prototype No. 11 and prototype No. 14 are fuel cell electrode materials 21 and 31 that are sufficiently practical, though somewhat inferior to the comparative sample (B) using platinum as a catalyst.
  • the fuel cell electrode materials 21 and 31 have insufficient electrical characteristics for use in the fuel cell 1a. This may be due to the following reasons.
  • the sintering temperature in trial production No11 is a molded body sintered at a temperature Hi higher than the temperature Lo.
  • a high temperature Hi sintering temperature 1100 to 1300 ° C .: center temperature around 1200 ° C.
  • Cu powder having a high electric conductivity melts and has a high melting point (a melting point higher than that of one transition metal).
  • Ni and Fe powders are Ni and Fe powders.
  • the sintering temperature is lower than the melting point 1084 ° C. of Cu, particularly on the inner side of the molded body.
  • the melting point 1084 ° C. of Cu since Cu does not melt, it is difficult to closely bond to other transition metal powders. That is, in the material 48Fe-48Ni-4Cu, it can be said that the superiority or inferiority of the prototype No11 and the prototype No12 as the fuel cell electrode material depends on the setting of the sintering temperature range during sintering.
  • the superiority and inferiority of the prototype No. 14 with the material 48Fe-48Ni-4Cu and the prototype No. 14 with the material Fe-48Ni-4Cu having a porosity close to 20% as the fuel cell electrode material can be said to be superior.
  • Fe-48Ni-4Cu containing Ni as a main component has slightly better characteristics than 48Fe-48Ni-4Cu containing Fe as a main component.
  • the correlation between the porosity of the molded body and the terminal voltage of the fuel cell 1a shows that the porosity of the molded body is within a certain range of porosity (20 to 40%). The higher the rate, the better the catalyst characteristics as a fuel cell electrode material.
  • the porosity of the molded body is in the range of 20% to 40% with respect to the volume of the molded body (or 100% relative density of the above-described metal plate that is the closest packed). This is because when the porosity is less than 20%, the permeability of fuel such as hydrogen gas or oxygen gas is decreased, and the surface area ratio of the void is also decreased. On the other hand, if the porosity exceeds 40%, the strength of the molded body becomes weak in the structural aspect of the molded body, and it is difficult to maintain sufficient strength.
  • Mg is 1 to 3 mass%
  • Zn is 2 to 3 mass%
  • Al is 5 to 5 mass%. It is preferable to include at least 6% by mass, including Ni, Fe, and Cr, with a total of mass% obtained by subtracting mass% of the contained metal from 100% by mass.
  • Ni, Fe, Cr, Mg Other examples including 1 to 3% by mass of Mg
  • Ni, Fe, Cr, Zn Other examples including 2 to 3% by mass of Zn 3)
  • Ni, Fe, Cr, Al A combination of a 3d transition metal containing 5 to 6% by mass of Al and the above metal was also found to be promising as a fuel cell electrode material.
  • the metal material used for the powder not only a single metal but also an alloy of two or more metals, for example, an alloy of Ni and Fe, may be used as a powder. Moreover, you may use the powder below a predetermined particle diameter.
  • the fuel cell electrode materials 21 and 31 support a luminescent material that emits light by infrared or ultraviolet light in a part between the gaps of the molded body, and when a counterfeit product of the product is produced, Provide a function that can determine the authenticity of the presence or absence.
  • the luminescent material or the like may be physically fitted in a part of the plurality of voids in the molded body, or may be fixed in the void by an adhesive or the like, and is embedded in a part of the surface of the molded body. You may do it.
  • the adhesive is not particularly limited, and a well-known one can be used.
  • the luminescent material can be fixed to the surface of the sintered molded body by a phenol resin adhesive, an epoxy resin adhesive, or the like.
  • the step of supporting the luminescent material is performed at a certain low temperature or less (a temperature not impairing the characteristics of the luminescent material), for example, in a cooling step after sintering or after completion of cooling. Addition and adhesion.
  • the luminescent substance is a substance that emits light by infrared rays, ultraviolet rays, or the like.
  • a light-emitting substance that emits light by ultraviolet rays or the like contains BaMg 2 Al 16 O 27 : Eu, BaMg 2 Al 16 O 27 : Eu, Mn, or the like as a main component.
  • the present invention shows a technique related to an electrode material for a fuel cell having an oxygen reduction ability without using a platinum group element.
  • SYMBOLS 1, 1a 100 ... Fuel cell 2, 2a, 200, 200a ... Fuel electrode 3, 3a, 300, 300a ... Air electrode, 4 ... PEM membrane, 5 ... Hydrogen gas inlet part, 6 ... Oxygen gas inlet part, DESCRIPTION OF SYMBOLS 11 ... Hydrogen gas supply connection part, 12 ... Oxygen gas supply connection part, 13 ... Water discharge part, 14 ... Electrode connection terminal, 15 ... Load, 21, 31 ... Electrode material for fuel cells, 22, 32 ... Conductive material, 23 33, holes, 201, 301 ... catalyst for electrodes

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Abstract

Le problème décrit par l'invention est de fournir un matériau d'électrode pour pile à combustible, utilisé comme couche de catalyseur d'électrode à combustible ou comme couche de catalyseur d'électrode à air, dans lequel aucun élément du groupe platine n'est utilisé, et un procédé de préparation du matériau d'électrode. La solution de l'invention, selon un mode de réalisation, porte sur des matériaux d'électrode (2, 3) pour pile à combustible qui comprennent un comprimé ne contenant aucun élément du groupe platine et comprenant du fer (Fe) comme constituant principal, le comprimé contenant au moins Fe et une pluralité de différents métaux de transition 3d comme matériaux métalliques. Le comprimé comprend un mélange comprenant une poudre de chacun des matériaux métalliques, et comporte des vides dispersés dans le comprimé de manière que de l'hydrogène et de l'oxygène utilisés dans une pile à combustible (1) puissent pénétrer dans le comprimé.
PCT/JP2016/083547 2015-11-20 2016-11-11 Matériau d'électrode pour pile à combustible, et son procédé de préparation WO2017086250A1 (fr)

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JP2019220340A (ja) * 2018-06-20 2019-12-26 株式会社グラヴィトン 電極
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JP7193109B2 (ja) * 2018-07-19 2022-12-20 グローバル・リンク株式会社 電極及び電極製造方法
JP2020019980A (ja) * 2018-07-31 2020-02-06 株式会社グラヴィトン 電気分解装置及び電極製造方法
JP7193111B2 (ja) * 2018-07-31 2022-12-20 グローバル・リンク株式会社 カーボンナノチューブ電極又はカーボンナノホーン電極及び電極製造方法
JP7281158B2 (ja) * 2018-07-31 2023-05-25 グローバル・リンク株式会社 固体高分子形燃料電池及び電極製造方法
JP7171024B2 (ja) * 2018-08-30 2022-11-15 グローバル・リンク株式会社 固体高分子形燃料電池の燃料極及び空気極の製造方法
JP2020035650A (ja) * 2018-08-30 2020-03-05 株式会社グラヴィトン 電極
JP7179314B2 (ja) * 2018-08-30 2022-11-29 グローバル・リンク株式会社 電気分解装置の陽極及び陰極の製造方法
JP2020047466A (ja) * 2018-09-19 2020-03-26 株式会社グラヴィトン 電極
JP7171027B2 (ja) * 2018-09-19 2022-11-15 グローバル・リンク株式会社 固体高分子形燃料電池の燃料極及び空気極の製造方法
JP7141695B2 (ja) * 2018-09-19 2022-09-26 グローバル・リンク株式会社 電気分解装置の陽極及び陰極の製造方法
JP2020064786A (ja) * 2018-10-18 2020-04-23 株式会社グラヴィトン 固体高分子形燃料電池
JP2020064784A (ja) * 2018-10-18 2020-04-23 株式会社グラヴィトン 電極及び電極製造方法
JP7262739B2 (ja) * 2018-11-29 2023-04-24 グローバル・リンク株式会社 電気分解装置の陽極及び陰極の製造方法

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