JP2020021577A - Polymer electrolyte fuel cell and manufacturing method of electrode - Google Patents

Abstract

To provide a polymer electrolyte fuel cell comprising a fuel electrode and an air electrode having a catalytic activity (catalysis) without using a platinum group element.SOLUTION: A fuel electrode 13A and an air electrode 14A of a polymer electrolyte fuel cell 10 are a carbon nanotube electrode 15A or a carbon nanohorn electrode 15B. Each of the electrodes 15A and 15B comprises: alloy fine particles of an alloy molded article obtained by compressing a mixture of transition metal fine powder obtained by uniformly mixing and dispersing transition metal powder of at least three kinds of transition metals selected from various kinds of transition metals, followed by burning; and aggregates of carbon nanotubes or carbon nanohorns. In the mixture of transition metal fine powder, at least three kinds of transition metals are selected from various kinds of transition metals so that a compound work function of work functions of at least three kinds of transition metals selected is approximated to a work function of the platinum group elements. In the electrodes 15A and 15B, alloy fine particles are carried on the surface of carbon nanotubes or the surface of carbon nanohorns.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a polymer electrolyte fuel cell provided with a cell stack having a plurality of cells, and also relates to a method of manufacturing a fuel electrode and an air electrode forming cells of the polymer electrolyte fuel cell.

  A solid polymer electrolyte membrane; an anode electrode and a cathode electrode sandwiching the solid polymer electrolyte membrane from both sides; a fuel container containing a liquid fuel; and a gas-liquid separating porous provided between the anode electrode and the cathode electrode. Having a fuel vaporization layer composed of a body and a perforated fixing plate sandwiching the fuel vaporization layer from both sides, wherein the aperture ratio of the perforated fixing plate disposed on the cathode electrode side is equal to that of the perforated fixing plate disposed on the anode electrode side. A polymer electrolyte fuel cell having a larger aperture ratio is disclosed (see Patent Document 1).

JP 2011-222119 A

The method for producing the cathode electrode and the anode electrode of the solid polymer fuel cell disclosed in Patent Document 1 is as follows. A catalyst-supporting carbon fine particle in which 55% by weight of platinum fine particles having a particle diameter in the range of 3 to 5 nm is supported on the carbon particle, and an appropriate amount of a 5% by weight Nafion solution is added to 1 g of the catalyst-supporting carbon fine particle, followed by stirring. Make a catalyst paste for the cathode electrode. A catalyst paste for a cathode electrode is applied on carbon paper as a base material in an amount of 8 mg / cm ² , and then dried to produce a 4 cm × 4 cm cathode electrode. Next, catalyst-loaded carbon fine particles carrying 55% by weight of platinum (Pt) -ruthenium (Ru) alloy fine particles (Ru ratio: 60 at%) having a particle diameter in the range of 3 to 5 nm instead of platinum fine particles. And an appropriate amount of a 5% by weight Nafion solution is added to 1 g of the catalyst-supporting carbon fine particles, followed by stirring to prepare a catalyst paste for an anode electrode. An anode electrode catalyst paste is applied on carbon paper as a base material in an amount of 8 mg / cm ² , and then dried to produce a 4 cm × 4 cm anode electrode.

  Various platinum-supported carbons are widely used as electrode catalysts for polymer electrolyte fuel cells. However, the platinum group element is a noble metal, and is a scarce resource with a limited production amount. Therefore, it is required to reduce the amount of the platinum group element used. Further, development of inexpensive fuel electrodes and air electrodes having a platinum-less catalyst using a material other than expensive platinum is required for the spread of polymer electrolyte fuel cells in the future.

  An object of the present invention is to provide a fuel electrode and an air electrode having catalytic activity (catalysis) without using a platinum group element, and to generate sufficient electricity using a platinum-less fuel electrode and an air electrode. An object of the present invention is to provide a polymer electrolyte fuel cell capable of supplying sufficient electric energy to a load. Another object of the present invention is to provide an electrode for producing a fuel electrode and an air electrode of a polymer electrolyte fuel cell which can be manufactured at low cost without using a platinum group element and has sufficient catalytic activity (catalysis). It is to provide a manufacturing method.

  A first premise of the present invention for solving the above problem is that an electrode assembly including a cell stack having a plurality of cells, wherein the cells are located between a fuel electrode and an air electrode, and between the fuel electrode and the air electrode This is a polymer electrolyte fuel cell formed from a membrane and separators located outside the fuel electrode and outside the air electrode.

  The feature of the polymer electrolyte fuel cell of the present invention on the first premise is that the fuel electrode and the air electrode are carbon nanotube electrodes or carbon nanohorn electrodes, and the carbon nanotube electrodes or carbon nanohorn electrodes are formed from various transition metals. A transition metal fine powder mixture obtained by uniformly mixing and dispersing transition metal fine powders of at least three kinds of selected transition metals is compressed, and then alloy fine particles of an alloy molded product which is baked, and aggregates of carbon nanotubes or carbon nanohorns are formed. The transition metal fine powder mixture, wherein at least three of the various transition metals are selected so that the composite work function of the work functions of the at least three selected transition metals is close to the work function of the platinum group element. Types of transition metals are selected, and for carbon nanotube electrodes or carbon nanohorn electrodes, In the Roy fine particles are carried on the surface or surfaces of the carbon nanohorn carbon nanotubes.

  As an example of the polymer electrolyte fuel cell of the present invention, on the surface of the carbon nanotube or the surface of the carbon nanohorn, an alloy fine particle laminated porous structure is formed by alloy fine particles overlapping outward from the surface of the carbon nanotube or the carbon nanohorn, In the polymer electrolyte fuel cell, the electrode assembly membrane and the alloy fine particle laminated porous structure overlap without any gap.

  As another example of the polymer electrolyte fuel cell of the present invention, the particle size of the transition metal fine powder is in the range of 10 μm to 200 μm, and the thickness of the carbon nanotube electrode or the carbon nanohorn electrode is 0.03 mm to 0 μm. 0.3 mm.

  In another example of the polymer electrolyte fuel cell according to the present invention, the transition metal fine powder mixture is mainly composed of Ni (nickel) fine powder, and the transition metal fine powder mixture excludes the work function of Ni and Ni. At least two other transition metals excluding Ni fine powder from various transition metals so that the composite work function with the work function of the other at least two transition metals approximates the work function of the platinum group element. Are selected.

  As another example of the polymer electrolyte fuel cell according to the present invention, the weight ratio of the fine powder of Ni (nickel) to the total weight of the transition metal fine powder mixture is in the range of 30% to 50%, The weight ratio of the transition metal fine powder of one transition metal excluding the powder to the total weight of the transition metal fine powder mixture is in the range of 20% to 50%, and at least one other transition metal excluding the Ni fine powder. The weight ratio of the transition metal fine powder of the metal to the total weight of the transition metal fine powder mixture is in the range of 3% to 20%.

  As another example of the polymer electrolyte fuel cell of the present invention, the transition metal fine powder mixture is mainly composed of Fe (iron) fine powder, and the transition metal fine powder mixture excludes the work function of Fe and Fe. At least two other transition metals excluding the fine powder of Fe from various transition metals so that the work function of the transition metal and the work function of the other at least two transition metals are close to the work function of the platinum group element. Are selected.

  As another example of the polymer electrolyte fuel cell according to the present invention, the weight ratio of the fine powder of Fe (iron) to the total weight of the transition metal fine powder mixture is in the range of 30% to 50%. The weight ratio of the transition metal fine powder of one type of transition metal excluding the powder to the total weight of the transition metal fine powder mixture is in the range of 20% to 50%, and at least one other transition metal excluding the fine powder of Fe The weight ratio of the metal transition metal powder to the total weight of the transition metal powder mixture is in the range of 3% to 20%.

  In another example of the polymer electrolyte fuel cell according to the present invention, the transition metal fine powder mixture mainly contains Cu (copper) fine powder, and the transition metal fine powder mixture excludes the work function of Cu and Cu. At least two other transition metals excluding the fine powder of Cu from various transition metals such that the work function of the other transition metals with the work function of the other at least two transition metals approximates the work function of the platinum group element. Are selected.

  As another example of the polymer electrolyte fuel cell of the present invention, the weight ratio of the fine powder of Cu (copper) to the total weight of the transition metal fine powder mixture is in the range of 30% to 50%, and the fine powder of Cu is used. The weight ratio of the transition metal fine powder of one type of transition metal excluding the powder to the total weight of the transition metal fine powder mixture is in the range of 20% to 50%, and at least one other transition excluding the fine powder of Cu. The weight ratio of the metal transition metal fine powder to the total weight of the transition metal fine powder mixture is in the range of 3% to 20%.

  As another example of the polymer electrolyte fuel cell of the present invention, in an alloy molding, transition metal fine powder of at least two types of transition metals among the selected transition metals is melted during firing of the transition metal fine powder mixture. The transition metal fine powder of the transition metal is joined using the molten transition metal fine powder of the transition metal as a binder.

  A second premise of the present invention for solving the above problems is an electrode manufacturing method for manufacturing a carbon nanotube electrode or a carbon nanohorn used as a fuel electrode and an air electrode of a polymer electrolyte fuel cell.

  The feature of the electrode manufacturing method of the present invention on the second premise is that the electrode manufacturing method is such that the work function of at least three types of transition metals selected from various transition metals is close to the work function of a platinum group element. A transition metal selection step of selecting at least three types of transition metals from various transition metals, and a transition metal fine powder of at least three types of transition metals selected in the transition metal selection step. A transition metal fine powder mixture producing step of forming a dispersed transition metal fine powder mixture, and a transition of producing a transition metal fine powder compact by pressing the transition metal fine powder mixture produced by the transition metal fine powder mixture producing step at a predetermined pressure. An alloy for sintering the transition metal fine powder compact produced by the metal fine powder compact production process and the transition metal fine powder compact production process at a predetermined temperature to form an alloy molded product. Forming a molded article, generating carbon nanotubes or carbon nanohorns, evaporating the alloy molded article formed by the alloy molded article forming step, and supporting the alloy fine particles of the alloy molded article on the surface of the carbon nanotube or the surface of the carbon nanohorn. And a step of supporting an alloy fine particle.

  As an example of the method for producing an electrode of a polymer electrolyte fuel cell of the present invention, the alloy fine particle supporting step is to evaporate an alloy molded product simultaneously with the generation of carbon nanotubes or carbon nanohorns, and to convert the alloy fine particles of the alloy molded product into carbon nanotubes. It is supported on the surface or the surface of the carbon nanohorn.

  As another example of the method for manufacturing an electrode of a polymer electrolyte fuel cell according to the present invention, the transition metal fine powder mixture preparing step includes the step of preparing at least three types of transition metals selected in the transition metal selection step with a particle size of 10 μm to 200 μm. Finely pulverize.

  As another example of the method for producing an electrode of a polymer electrolyte fuel cell according to the present invention, the transition metal fine powder compact production step is performed by using the transition metal fine powder mixture produced by the transition metal fine powder mixture production step at 500 Mpa to 800 Mpa. To produce a compressed transition metal fine powder.

  As another example of the method for producing an electrode of a polymer electrolyte fuel cell according to the present invention, an alloy molded article forming step includes a transition metal fine powder of at least two kinds of transition metals selected from the transition metals selected in the transition metal selecting step. The transition metal fine powder compact is fired at a temperature at which the body is melted, and the transition metal fine powder of the transition metal is joined using the transition metal fine powder of the molten transition metal as a binder.

  As another example of the method for producing an electrode of a polymer electrolyte fuel cell of the present invention, the alloy fine particle supporting step comprises forming a carbon nanotube electrode or a carbon nanohorn electrode into a thickness dimension in a range of 0.03 mm to 0.3 mm, An alloy fine particle laminated porous structure is formed by alloy fine particles overlapping outward from the surface of the carbon nanotube or the surface of the carbon nanohorn.

  According to the polymer electrolyte fuel cell according to the present invention, the carbon nanotube electrode or the carbon nanohorn electrode as the fuel electrode and the air electrode used therein is a transition metal of at least three kinds of transition metals selected from various transition metals. At least three selected types including alloy fine particles of an alloy molded product that is fired after compressing a transition metal fine powder mixture in which fine powders are uniformly mixed and dispersed, and an aggregate of carbon nanotubes or an aggregate of carbon nanohorns At least three types of transition metals are selected from various transition metals so that the composite work function of the work function of the transition metal approximates the work function of the platinum group element, and the alloy fine particles are formed on the surface of the carbon nanotube or on the carbon nanohorn. Since it is supported on the surface, the surface of the carbon nanotube or the surface of the carbon nanohorn A carbon nanotube electrode (fuel electrode and air electrode) or a carbon nanohorn electrode (fuel electrode and air electrode) carrying alloy fine particles on the surface thereof has substantially the same work function as a fuel electrode and an air electrode containing a platinum group element; Can exhibit substantially the same catalytic activity (catalysis) as the fuel electrode and the air electrode containing Pt, and generate sufficient electricity in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or a carbon nanohorn electrode. In addition, sufficient electric energy can be supplied to the load connected to the polymer electrolyte fuel cell. In the polymer electrolyte fuel cell, the carbon nanotube electrode (fuel electrode and air electrode) or the carbon nanohorn electrode (fuel electrode and air electrode) used therein has at least three types of transition metals selected from various transition metals. Utilizing alloy fine particles (alloy molded product) made of metal fine powder, it is a platinum-less alloy that does not use expensive platinum group elements, and a polymer electrolyte fuel cell can be manufactured at low cost.

  The alloy fine particle laminated porous structure is formed on the surface of the carbon nanotube or the carbon nanohorn by the alloy fine particles overlapping outward from the surface of the carbon nanotube or the carbon nanohorn, and the electrode assembly film and the alloy fine particle laminated porous structure overlap without any gap. The polymer electrolyte fuel cell that is used can increase the specific surface area of the alloy fine particles by forming a porous structure of the alloy fine particles on the surface of the carbon nanotube or the surface of the carbon nanohorn, and sufficiently enhance the catalytic action of the alloy fine particles. And the carbon nanotube electrode (fuel electrode and air electrode) or the carbon nanohorn electrode (fuel electrode and air electrode) having the porous structure of the alloy fine particles are almost the same as the fuel electrode and air electrode containing a platinum group element. No A polymer electrolyte fuel cell using a platinum-free carbon nanotube electrode or carbon nanohorn electrode that has a function and can exhibit substantially the same catalytic activity (catalysis) as a fuel electrode and an air electrode containing a platinum group element. And sufficient electric energy can be supplied to a load connected to the polymer electrolyte fuel cell.

  The polymer electrolyte fuel cell in which the transition metal fine particles have a particle size in the range of 10 μm to 200 μm and the thickness of the carbon nanotube electrode or carbon nanohorn electrode is in the range of 0.03 mm to 0.3 mm is a carbon nanotube electrode or By setting the thickness dimension of the carbon nanohorn electrode within the above range, the electrical resistance of the carbon nanotube electrode (fuel electrode and air electrode) or the carbon nanohorn electrode (fuel electrode and air electrode) can be reduced, and the carbon nanotube electrode or carbon Since the current flows smoothly through the nanohorn electrode, sufficient electricity can be generated in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or a carbon nanohorn electrode, and connected to the polymer electrolyte fuel cell. Supply sufficient electrical energy to the Can be paid.

  The transition metal fine powder mixture is mainly composed of Ni (nickel) fine powder, and the work function of Ni and the work function of at least two types of transition metals other than Ni is a work function of a platinum group element. As an approximation, a polymer electrolyte fuel cell in which transition metal fine powder of at least two other transition metals other than the fine powder of Ni is selected from various transition metals, the work function of Ni and the Ni And at least two other transition metals excluding Ni fine powder from various transition metals so that the work function of the transition metal and the work function of at least two other transition metals other than the above is close to the work function of the platinum group element. Since the fine powder of the transition metal is selected, the carbon nanotube electrode (fuel powder) having the alloy fine particles or the alloy fine particle laminated porous structure is formed on the surface of the carbon nanotube or the surface of the carbon nanohorn. Electrode and air electrode) or a carbon nanohorn electrode (fuel electrode and air electrode) has substantially the same work function as the fuel electrode and air electrode containing a platinum group element, and is substantially the same as the fuel electrode and air electrode containing a platinum group element. It is capable of exhibiting catalytic activity (catalysis), can generate sufficient electricity in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or a carbon nanohorn electrode, and has a solid polymer fuel cell. Sufficient electrical energy to the load connected to the load.

  The weight ratio of the Ni (nickel) fine powder to the total weight of the transition metal fine powder mixture is in the range of 30% to 50%, and the transition metal fine powder of one type of transition metal fine powder excluding the Ni fine powder The weight ratio of the transition metal fine powder of at least one other transition metal excluding the Ni fine powder to the total weight of the transition metal fine powder mixture is in the range of 20% to 50% with respect to the total weight of the body mixture. Is in the range of 3% to 20%, the composite work function of the work function of Ni and the work function of at least two types of transition metals other than Ni is the work function of the platinum group element. As an approximation, at least two types of transition metal fine powder excluding Ni fine powder are selected from various transition metals, and the weight ratio of Ni fine powder and Ni fine powder are excluded. At least one transition By setting the weight ratio of the fine metal powder and the weight ratio of at least one type of transition metal fine powder other than the fine Ni powder to the above ranges, the carbon nanotube electrode (fuel Electrode and air electrode) or a carbon nanohorn electrode (fuel electrode and air electrode) has substantially the same work function as a fuel electrode and an air electrode containing a platinum group element, and a carbon nanotube electrode or a carbon nanohorn electrode contains a platinum group element. It exhibits substantially the same catalytic activity (catalysis) as the electrode and the air electrode, and can generate sufficient electricity in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or a carbon nanohorn electrode. Sufficient electric energy can be supplied to the load connected to the molecular fuel cell.

  The transition metal fine powder mixture is mainly composed of a fine powder of Fe (iron), and the work function of Fe and the work function of at least two types of transition metals other than Fe is a work function of a platinum group element. As an approximation, a polymer electrolyte fuel cell in which at least two transition metal fine powders other than the fine powder of Fe are selected from among various transition metals, the work function of Fe and Fe And at least two other types of transition metals excluding the fine powder of Fe from various transition metals so that the composite work function with the work function of at least two other types of transition metals other than the above is similar to the work function of the platinum group element. Since the transition metal fine powder is selected, the carbon nanotube electrode (the fuel electrode and the like) having the alloy fine particles or the alloy fine particle laminated porous structure on the surface of the carbon nanotube or the surface of the carbon nanohorn is selected. The air electrode) or the carbon nanohorn electrode (fuel electrode and air electrode) has substantially the same work function as the fuel electrode and the air electrode containing a platinum group element, and has almost the same catalytic activity as the fuel electrode and the air electrode containing a platinum group element. (Catalytic action), and can generate sufficient electricity in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or carbon nanohorn electrode, and can be connected to a polymer electrolyte fuel cell Enough electrical energy to the applied load.

  The weight ratio of the fine powder of Fe (iron) to the total weight of the transition metal fine powder mixture is in the range of 30% to 50%, and the transition metal fine powder of the transition metal fine powder of one type of transition metal excluding the fine powder of Fe The weight ratio of the transition metal fine powder of at least one other transition metal excluding the Fe fine powder to the total weight of the transition metal fine powder mixture is in the range of 20% to 50% with respect to the total weight of the body mixture. Is in the range of 3% to 20%, the composite work function of the work function of Fe and the work function of at least two types of transition metals other than Fe is the work function of the platinum group element. As an approximation, at least two types of transition metal fine powder except for the fine powder of Fe are selected from various transition metals, and the weight ratio of the fine powder of Fe and the fine powder of Fe are excluded. At least one transition metal By setting the weight ratio of the fine powder and the weight ratio of at least one type of transition metal other than the fine powder of Fe within the above ranges, the carbon nanotube electrode (the fuel electrode and the The air electrode) or the carbon nanohorn electrode (fuel electrode and air electrode) has substantially the same work function as the fuel electrode and the air electrode containing a platinum group element, and the carbon nanotube electrode or the carbon nanohorn electrode has a fuel electrode containing a platinum group element and It exhibits almost the same catalytic activity (catalysis) as an air electrode, and can generate sufficient electricity in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or a carbon nanohorn electrode. Sufficient electric energy can be supplied to the load connected to the fuel cell.

  The transition metal fine powder mixture contains Cu (copper) fine powder as a main component, and the composite work function of the work function of Cu and the work function of at least two types of transition metals other than Cu becomes the work function of the platinum group element. As an approximation, a polymer electrolyte fuel cell in which at least two transition metal fine powders of at least two other transition metals except for the fine powder of Cu are selected from various transition metals, the work function of Cu and the Cu And at least two other types of transition metals excluding the fine powder of Cu from various transition metals so that the work function thereof with the work function of the other at least two types of transition metals other than that of the transition metal approximates the work function of the platinum group element. Since the transition metal fine powder is selected, the carbon nanotube electrode (the fuel electrode and the like) having the alloy fine particles or the alloy fine particle laminated porous structure on the surface of the carbon nanotube or the surface of the carbon nanohorn is selected. The air electrode) or the carbon nanohorn electrode (fuel electrode and air electrode) has substantially the same work function as the fuel electrode and the air electrode containing a platinum group element, and has almost the same catalytic activity as the fuel electrode and the air electrode containing a platinum group element. (Catalytic action), and can generate sufficient electricity in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or carbon nanohorn electrode, and can be connected to a polymer electrolyte fuel cell Enough electrical energy to the applied load.

  The weight ratio of the fine powder of Cu (copper) to the total weight of the transition metal fine powder mixture is in the range of 30% to 50%, and the transition metal fine powder of the transition metal fine powder of one type of transition metal excluding the fine powder of Cu The weight ratio of the transition metal fine powder of at least one other transition metal excluding the Cu fine powder to the total weight of the transition metal fine powder mixture is in the range of 20% to 50% with respect to the total weight of the body mixture. Is in the range of 3% to 20%, the composite work function of the work function of Cu and the work function of at least two types of transition metals other than Cu is the work function of the platinum group element. As an approximation, at least two types of transition metal fine powder excluding Cu fine powder are selected from various transition metals, and the weight ratio of Cu fine powder and Cu fine powder are excluded. At least one transition metal By setting the weight ratio of the fine powder and the weight ratio of the fine powder of at least one other type of transition metal excluding the fine powder of Cu to the above ranges, the carbon nanotube electrode (fuel electrode and The air electrode) or the carbon nanohorn electrode (fuel electrode and air electrode) has substantially the same work function as the fuel electrode and the air electrode containing a platinum group element, and the carbon nanotube electrode or the carbon nanohorn electrode has a fuel electrode containing a platinum group element and It exhibits almost the same catalytic activity (catalysis) as an air electrode, and can generate sufficient electricity in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or a carbon nanohorn electrode. Sufficient electric energy can be supplied to the load connected to the fuel cell.

  In the alloy molded product, transition metal fine powder of at least two types of transition metals among the selected transition metals is melted at the time of firing the transition metal fine powder mixture, and the transition metal fine powder of the molten transition metal is used as a binder. The polymer electrolyte fuel cell to which the transition metal fine powder of the metal is joined can produce an alloy molded article by melting the transition metal fine powder of at least two kinds of transition metals among the transition metals. Since the alloy fine particles of the molded product can be supported on the surface of the carbon nanotube or the surface of the carbon nanohorn, and the alloy fine particle laminated porous structure can be formed on the surface of the carbon nanotube or the surface of the carbon nanohorn, the carbon nanotube electrode ( Fuel electrode and air electrode) or carbon nanohorn electrode (fuel electrode and air) Electrode) exhibits substantially the same catalytic activity (catalysis) as a fuel electrode containing a platinum group element and an air electrode, and provides sufficient electricity in a polymer electrolyte fuel cell using a platinum-less carbon nanotube electrode or carbon nanohorn electrode. Can be generated, and sufficient electric energy can be supplied to the load connected to the polymer electrolyte fuel cell.

  According to the method for producing a carbon nanotube electrode or a carbon nanohorn electrode used as the fuel electrode and the air electrode of the polymer electrolyte fuel cell according to the present invention, the work function of at least three types of transition metals selected from various transition metals is selected. A transition metal selecting step of selecting at least three types of transition metals from various transition metals so that the synthetic work function approximates the work function of the platinum group element; and at least three types of transition metals selected by the transition metal selecting step. A transition metal fine powder mixture forming step of uniformly mixing and dispersing transition metal fine particles of the transition metal to form a transition metal fine powder mixture; and a transition metal fine powder mixture produced by the transition metal fine powder mixture forming step at a predetermined pressure. Pressurized transition metal fine powder compressed product making process to make transition metal fine powder compressed product, and transition metal fine powder compressed product making process An alloy molded article producing step of firing the compressed transition metal fine powder at a predetermined temperature to form an alloy molded article, and generating carbon nanotubes or carbon nanohorns and evaporating the alloy molded article produced by the alloy molded article producing step. A carbon nanotube electrode (a fuel electrode and an air electrode) or a carbon nanohorn electrode (a fuel electrode and an air electrode) from the alloy fine particle supporting step of supporting the alloy fine particles of the alloy molded article on the surface of the carbon nanotube or the surface of the carbon nanohorn. A carbon nanotube electrode (a fuel electrode and an air electrode) or a carbon nanohorn electrode (a fuel electrode and an air electrode) used for a platinum-free polymer electrolyte fuel cell that does not use a platinum group element can be produced at low cost, and catalytic activity (Catalytic action) enables the catalytic function to be used sufficiently and reliably There, it is possible to make the carbon nanotube electrodes or carbon nanohorn electrode capable of generating sufficient electricity in the solid polymer fuel cell.

  The alloy fine particle supporting step evaporates the alloy molded product at the same time as the formation of the carbon nanotubes or carbon nanohorns, and manufactures the electrode of a polymer electrolyte fuel cell in which the alloy fine particles of the alloy molded product are supported on the surface of the carbon nanotube or carbon nanohorn. Since the method is to evaporate the alloy molded product while generating carbon nanotubes or carbon nanohorns and to carry the alloy fine particles of the alloy molded product on the surface of the carbon nanotube or the surface of the carbon nanohorn, the method is applied to the surface of the carbon nanotube or the surface of the carbon nanohorn. A platinum-free carbon nanotube electrode (fuel electrode) in which alloy fine particles can be supported in a state of being uniformly dispersed, and alloy fine particles are uniformly dispersed and supported on the surface of a carbon nanotube or the surface of a carbon nanohorn. And a carbon nanohorn electrode (fuel electrode and air electrode) can be manufactured at low cost, and the catalyst function can be used sufficiently and reliably, and has excellent catalytic activity (catalysis). A bon nanotube electrode or a carbon nanohorn electrode that can be suitably used for a polymer electrolyte fuel cell can be produced.

  The method for producing an electrode of a polymer electrolyte fuel cell, wherein the transition metal fine powder mixture preparing step pulverizes at least three types of transition metals selected in the transition metal selection step to a particle size of 10 μm to 200 μm, comprises: An alloy molded product can be made by finely pulverizing the alloy molded product to a particle size of platinum. An excellent catalyst that can produce a carbon nanotube electrode (a fuel electrode and an air electrode) or a carbon nanohorn electrode (a fuel electrode and an air electrode) at a low cost, and can use the catalyst function sufficiently and reliably. Carbon nanotube electrode or carbohydrate having activity (catalysis) and suitable for use in polymer electrolyte fuel cells A nanohorn electrode can be made.

  A transition polymer fine powder compact is formed by applying a pressure of 500 Mpa to 800 Mpa to the transition metal fine powder mixture produced by the transition metal fine powder mixture production process to produce a transition metal fine powder compact. In the electrode manufacturing method, a transition metal fine powder compact can be produced by pressurizing (compressing) the transition metal fine powder mixture at a pressure within the above range, and firing the transition metal fine powder compact to form an alloy. And a platinum-less carbon nanotube electrode (a fuel electrode and an air Electrode) or carbon nanohorn electrodes (fuel electrode and air electrode) can be made at low cost, and the catalyst function can be used sufficiently and reliably. It can be made suitably carbon nanotube electrodes or carbon nanohorn electrode that can be used in a solid polymer fuel cell having a a possible excellent catalytic activity (catalytic).

  The alloy molded article preparation step is to fire the transition metal fine powder compact at a temperature at which the transition metal fine powder of at least two kinds of transition metals selected from the transition metals selected in the transition metal selection step is melted, The method for manufacturing an electrode of a polymer electrolyte fuel cell in which the transition metal fine powder of the transition metal is joined with the transition metal fine powder as a binder, the transition metal fine powder of at least two types of transition metals among the transition metals is melted. A platinum-less carbon nanotube electrode (fuel electrode) in which an alloy molded product can be produced by evaporating the alloy molded product and uniformly dispersing and carrying alloy fine particles of the alloy molded product on the surface of the carbon nanotube or the surface of the carbon nanohorn. And air electrode) or carbon nanohorn electrode (fuel electrode and air electrode) at low cost To produce a bon-nanotube electrode or a carbon nanohorn electrode which can be used sufficiently and reliably and has excellent catalytic activity (catalysis) and can be suitably used for polymer electrolyte fuel cells Can be.

  The alloy fine particle supporting step forms the carbon nanotube electrode or the carbon nanohorn electrode into a thickness dimension in the range of 0.03 mm to 0.3 mm, and laminates the alloy fine particles by the alloy fine particles overlapping outward from the surface of the carbon nanotube or the surface of the carbon nanohorn. The method for producing an electrode of a polymer electrolyte fuel cell that forms a porous structure can form an alloy fine particle-laminated porous structure on the surface of a carbon nanotube or the surface of a carbon nanohorn by evaporating an alloy molded product. A platinum-free carbon nanotube electrode (fuel electrode and air electrode) or carbon nanohorn electrode (fuel electrode and air electrode) having an alloy fine powder laminated porous structure with a large surface area can be manufactured at low cost. The electrode manufacturing method can reduce the electrical resistance of the carbon nanotube electrode or the carbon nanohorn electrode by setting the thickness dimension of the carbon nanotube electrode or the carbon nanohorn electrode in the above range, and can flow a current smoothly. A platinum-free carbon nanotube electrode or carbon nanohorn electrode capable of generating sufficient electricity in a polymer electrolyte fuel cell can be produced.

1 is a perspective view of a polymer electrolyte fuel cell shown as an example. FIG. 2 is an exploded perspective view showing an example of a cell forming a cell stack. The side view of a cell. The perspective view of the carbon nanotube electrode or the carbon nanohorn electrode shown as an example. FIG. 2 is a partially enlarged front view of a carbon nanotube electrode or a carbon nanohorn electrode shown as an example. FIG. 2 is a conceptual diagram of a carbon nanotube shown as an example carrying alloy fine particles. FIG. 2 is a conceptual diagram of a carbon nanohorn shown as an example carrying alloy fine particles. FIG. 9 is a partially enlarged front view of a carbon nanotube electrode or a carbon nanohorn electrode shown as another example. FIG. 3 is a conceptual diagram of a carbon nanotube shown as another example carrying alloy fine particles. FIG. 5 is a conceptual diagram of a carbon nanohorn shown as another example carrying alloy fine particles. The figure explaining the electric power generation of a polymer electrolyte fuel cell. The figure which shows the result of the electromotive force test of a carbon nanotube electrode or a carbon nanohorn electrode. The figure which shows the result of the IV characteristic test of a carbon nanotube electrode or a carbon nanohorn electrode. The figure explaining the manufacturing method of a carbon nanotube electrode or a carbon nanohorn electrode.

  Referring to the accompanying drawings such as FIG. 1 which is a perspective view of a polymer electrolyte fuel cell 10 shown as an example, a polymer electrolyte fuel cell according to the present invention and a carbon nanotube electrode 15A used in the polymer electrolyte fuel cell The details of the method for manufacturing the electrodes (the fuel electrodes 13A and 13B and the air electrodes 14A and 14B) or the carbon nanohorn electrodes 15B (the fuel electrodes 13A and 13B and the air electrodes 14A and 14B) will be described below. FIG. 2 is an exploded perspective view showing an example of the cell 11 forming the cell stack 12, and FIG. 3 is a side view of the cell 11. FIG. 4 is a perspective view of carbon nanotube electrodes 15A and 15B (fuel electrodes 13A and 13B and air electrodes 14A and 14B) or carbon nanohorn electrodes 15A and 15B (fuel electrodes 13A and 13B and air electrodes 14A and 14B) shown as examples. is there. In FIG. 4, the thickness direction is indicated by an arrow X, and the radial direction is indicated by an arrow Y.

  The polymer electrolyte fuel cell 10 includes a cell stack 12 (fuel cell stack) having a plurality of cells 11, and generates electricity (generates electric energy) by supplying hydrogen and oxygen. In the cell stack 12, a plurality of cells 11 (single cells) overlap in one direction and are connected in series. As an example of the cell 11, as shown in FIG. 2, a fuel electrode 13A (or fuel electrode 13B) (carbon nanotube electrode 15A or carbon nanohorn electrode 15B) and an air electrode 14A (or air electrode 14B) (carbon nanotube electrode 15A) Alternatively, the solid polymer electrolyte membrane 16 (electrode assembly membrane) (sulfonate) is located (interposed) between the fuel electrode 13A (or fuel electrode 13B) and the air electrode 14A (or air electrode 14B) and the carbon nanohorn electrode 15B). Group), a separator 17 (bipolar plate) positioned outside the fuel electrode 13A (or fuel electrode 13B) in the thickness direction, and a separator 17 positioned outside the air electrode 14A (or the air electrode 14B) in the thickness direction. And a separator 18 (bipolar plate).

  The separators 17 and 18 are provided with a supply channel (engraved) for supplying a reaction gas (hydrogen, oxygen, or the like). In the cell 11, as shown in FIG. 3, the fuel electrodes 13A and 13B, the air electrodes 14A and 14B, and the solid polymer electrolyte membrane 16 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly 19 (Membrane Electrode Assembly, MEA). ), And the membrane / electrode assembly 19 is sandwiched between the separators 17 and 18. The solid polymer electrolyte membrane 16 has proton conductivity and no electronic conductivity. A gas diffusion layer 21 is formed between the fuel electrode 13A (or the fuel electrode 13B) and the separator 17, and a gas diffusion layer 22 is formed between the air electrode 14A (or the air electrode 14B) and the separator 18. Have been. A gas seal 22 is provided between the fuel electrode 13A (or the fuel electrode 13B) and the separator 17 and above and below the gas diffusion layer 20. A gas seal 23 is provided between the air electrode 14A (or the air electrode 14B) and the separator 18 and above and below the gas diffusion layer 21.

  Fuel electrodes 13A and 13B (carbon nanotube electrode 15A or carbon nanohorn electrode 15B) and air electrodes 14A and 14B (carbon nanotube electrode or 15A, or carbon nanohorn electrode 15B) used in polymer electrolyte fuel cell 16 (cell 11) are: As shown in FIG. 4, it has a front surface 24 and a rear surface 25, has a predetermined area and a predetermined thickness L1, and has a planar shape of a square. The planar shape of the fuel electrode 13A (or the fuel electrode 13B) or the air electrode 14A (or the air electrode 14B) is not particularly limited. In addition to a square, other shapes such as a circle, an ellipse, and a polygon may be used according to the application. Can be formed into any planar shape.

  The fuel electrodes 13A, 13B (carbon nanotube electrode 15A or carbon nanohorn electrode 15B) and the air electrodes 14A, 14B (carbon nanotube electrodes 15A, 15B or carbon nanohorn electrodes 15A, 15B) are formed of an alloy 42 (alloy molding). From the fine particles 26 (alloy fine particles), the metal electrode thin plate 27 or the carbon electrode thin plate 28, and the aggregate 30 of carbon nanotubes 29 (aggregate plate) of predetermined area or the aggregate 32 of carbon nanohorn 31 of predetermined area (aggregate plate) Is formed. An alloy molded product 42 (alloy molded product) (see FIG. 14) is a uniform transition metal fine powder 39 of at least three types of transition metals 38 selected from various transition metals 38 processed (pulverized) into powder. The transition metal fine powder mixture 40 (see FIG. 14) mixed and dispersed is compressed and fired (sintered).

  The alloy compact 42 (alloy compact) is finely pulverized into an alloy fine powder 43 (alloy fine powder) having a particle size of 10 μm to 200 μm. From the fine particles 26 (alloy fine particles), the metal electrode thin plate 27 or the carbon electrode thin plate 28 and the aggregate 30 of carbon nanotubes 29 (aggregate plate) of a predetermined area or the aggregate 32 of carbon nanohorns 31 (aggregate plate) of a predetermined area. May be formed.

  As the transition metal 38, a 3d transition metal or a 4d transition metal is used. As the 3d transition metal, Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), and Zn (zinc) are used. Nb (niobium), Mo (molybdenum), and Ag (silver) are used as the 4d transition metal. The transition metal fine powder 39 of the transition metal 38 includes powdered (finely crushed) Ti (titanium) fine powder, powdered (finely crushed) Cr (chromium) fine powder, and powdery processed (Finely pulverized) Mn (manganese) fine powder, powdery (finely pulverized) Fe (iron) fine powder, powdery (finely pulverized) Co (cobalt) fine powder, powdery Processed (finely pulverized) Ni (nickel) fine powder, powdered (finely pulverized) Cu (copper) fine powder, powdered (finely pulverized) Zn (zinc) fine powder, powdery Nb (niobium) fine powder processed (finely pulverized), Mo (molybdenum) fine powder processed (pulverized) into powder, and Ag (silver) fine powder processed into powder are used.

  Fine powder of Ti (Ti processed into a powder (finely pulverized)), fine powder of Cr (Cr processed into a powder (fine pulverized)), and fine powder of Mn (processed into a powder (pulverized)) Mn), fine powder of Fe (Fe that has been processed (pulverized) into powder), fine powder of Co (Co that has been processed (pulverized) into powder), and fine powder of Ni (processed into powder ( Ni) finely pulverized), fine powder of Cu (Cu finely processed (finely pulverized)), fine powder of Zn (Zn finely processed (finely pulverized)), fine powder of Nb (powder Nb processed into a shape (finely pulverized), Mo fine powder (Mo processed into a fine powder (finely pulverized)), and Ag fine powder (Ag processed into a powder shape (finely pulverized)) Is in the range of 10 μm to 200 μm.

  In the transition metal fine powder mixture 40 (alloy molded product 42), the work function of at least three kinds of selected transition metals 38 (energy required to extract electrons from the substance) is the work function of the platinum group element. , At least three types of transition metals 38 are selected from among the transition metals 38. The work function of Ti is 4.14 (eV), the work function of Cr is 4.5 (eV), the work function of Mn is 4.1 (eV), and the work function of Fe is 4.67 (eV). ), The work function of Co is 5.0 (eV), the work function of Ni is 5.22 (eV), the work function of Cu is 5.10 (eV), and the work function of Zn is 3.63. (EV), the work function of Nb is 4.01 (eV), the work function of Mo is 4.45 (eV), and the work function of Ag is 4.31 (eV). The work function of platinum is 5.65 (eV).

  As an example of the transition metal fine powder mixture 40, Ni (nickel) fine powder processed into fine powder (finely pulverized) is used as a main component, and processed into fine powder except Ni fine powder and Ni (finely pulverized). And at least two other transition metals (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Fe (iron), powder Co (cobalt), Transition metal fine powder of powdered Cu (copper), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver)) The transition metal fine powder mixture 40 is obtained by uniformly mixing and dispersing the transition metal fine powder 39 with the body 39.

  A transition metal fine powder mixture 40 obtained by mixing Ni (nickel) fine powder as a main component and transition metal fine powder 39 of at least two other types of transition metals 38 other than Ni has a work function of Ni and excludes Ni. At least two other types of transition metals 38 excluding the fine Ni powder so that the composite work function with the work function of the other at least two types of transition metals 38 approximates the work function of the platinum group element. The transition metal fine powder 39 of the transition metal 38 is selected.

  In the alloy molded article 42 containing Ni fine powder as a main component, the transition metal fine powder 39 of at least two kinds of the transition metals 38 among the selected transition metals 38 is melted when the transition metal fine powder mixture 40 is fired, The transition metal fine powder 39 of the transition metal 38 is joined using the molten transition metal fine powder 39 of the transition metal 38 as a binder. The alloy fine powder 43 formed by finely pulverizing the alloy molded product 42 containing Ni as a main component is formed by compressing a transition metal fine powder mixture 40 containing Ni fine powder as a main component and then firing the mixture. The obtained alloy molded product 42 is finely pulverized with a particle size of 10 μm to 200 μm.

  In the transition metal fine powder mixture 40 mainly composed of Ni (nickel) fine powder, the weight ratio of the Ni fine powder to the total weight of the transition metal fine powder mixture 40 is in the range of 30% to 50%. Transition metal fine powder 39 of one kind of transition metal 38 excluding fine powder (Ti (titanium) fine powder, Cr (chromium) fine powder, Mn (manganese) fine powder, Fe (iron) fine powder, Co (cobalt) fine powder Transition metal fine powder mixture 40 of at least one of powder, Cu (copper) fine powder, Zn (zinc) fine powder, Nb (niobium) fine powder, Mo (molybdenum) fine powder, and Ag (silver) fine powder And a transition metal fine powder 39 (Ti (titanium) fine powder, Cr (chromium)) of at least one other type of transition metal 38 excluding the Ni fine powder. Fine powder, Mn (manganese Fine powder, Fe (iron) fine powder, Co (cobalt) fine powder, Cu (copper) fine powder, Zn (zinc) fine powder, Nb (niobium) fine powder, Mo (molybdenum) fine powder, Ag (silver) fine powder The weight ratio of the transition metal fine powder mixture 40 (the other at least one of the bodies) to the total weight is in the range of 3% to 20%.

  As a specific example of the alloy molded product 42 containing Ni (nickel) as a main component, a transition metal fine powder mixture 40 in which fine Ni powder, fine Cu powder, and fine ZN powder are uniformly mixed and dispersed is compressed. This is a sintered alloy molded product 42. As a specific example of the alloy fine powder 42 containing Ni as a main component (alloy fine powder containing Ni as a main component), Ni fine powder, Cu fine powder, and ZN fine powder are uniformly mixed and dispersed. The transition metal fine powder mixture 40 is compressed and fired to form an alloy molded product 42, and the alloy molded product 42 is finely pulverized with a particle size of 10 μm to 200 μm.

  The alloy molded product 42 (alloy fine powder 43) has a weight ratio of the Ni fine powder to the total weight of the transition metal fine powder mixture 40 of 48%, and the weight of the Cu fine powder to the total weight of the transition metal fine powder mixture 40. The ratio is 42%, and the weight ratio of the Zn fine powder to the total weight of the transition metal fine powder mixture 40 is 10%. Since the melting point of Ni is 1455 ° C., the melting point of Cu is 1084.5 ° C., and the melting point of Zn is 419.85 ° C., the fine powder of Zn and the fine powder of Cu are melted. Ni fine powder is joined as a binder.

  As another specific example of the alloy molded product 42 containing Ni (nickel) as a main component, a transition metal fine powder mixture 40 obtained by uniformly mixing and dispersing Ni fine powder, Mn fine powder, and Mo fine powder is compressed. An alloy molded article 42 fired after firing. Further, as another specific example of the alloy fine powder 43 containing Ni as a main component (alloy fine powder containing Ni as a main component), Ni fine powder, Mn fine powder, and Mo fine powder are uniformly mixed. The dispersed transition metal fine powder mixture 40 is compressed and fired to form an alloy molded product 42. The alloy molded product 42 is finely pulverized with a particle size of 10 μm to 200 μm.

  In the alloy molded product 42 (alloy fine powder), the weight ratio of the Ni fine powder to the total weight of the transition metal fine powder mixture 40 was 48%, and the weight ratio of the Mn fine powder to the total weight of the transition metal fine powder mixture 40. Is 7%, and the weight ratio of the Mo fine powder to the total weight of the transition metal fine powder mixture 40 is 45%. Since the melting point of Ni is 1455 ° C., the melting point of Mn is 1246 ° C., and the melting point of Mo is 2623 ° C., the Mn fine powder and the Ni fine powder are melted, and the melted Mn and Ni fine powder serve as a binder. Mo fine powder is joined.

  As another example of the transition metal fine powder mixture 40, a fine powder of Fe (iron) processed into a powder (fine pulverized) is used as a main component, and a fine powder of Fe and a powder excluding Fe are processed (fine pulverized). ) Other transition metals 38 (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Co (cobalt), powder Ni ( Nickel), powdered Cu (copper), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), and powdered Ag (silver)). A transition metal fine powder mixture 40 in which the transition metal fine powder 39 is uniformly mixed and dispersed.

  A transition metal fine powder mixture 40 obtained by mixing a fine powder of Fe (iron) as a main component and a transition metal fine powder 39 of at least two other types of transition metals 38 excluding Fe has a work function of Fe and excluding Fe. At least two other types of transition metals 38 excluding the fine powder of Fe from the various transition metals 38 so that the work function of the transition metal 38 and the work function of the other at least two types of transition metals 38 approximate the work function of the platinum group element. The transition metal fine powder 39 of the transition metal 38 is selected.

  In the alloy molding 42 mainly containing Fe fine powder, the transition metal fine powder 39 of at least two kinds of transition metals 38 of the selected transition metals 38 is melted at the time of firing the transition metal fine powder mixture 40, The transition metal fine powder 39 of the transition metal 38 is joined using the molten transition metal fine powder 39 of the transition metal 38 as a binder. The alloy fine powder 43 made by finely pulverizing the alloy molded product 42 containing Fe as a main component is formed by compressing a transition metal fine powder mixture 40 containing Fe fine powder as a main component, followed by firing. The obtained alloy molded product 42 is finely pulverized with a particle size of 10 μm to 200 μm.

  In the transition metal fine powder mixture 40 mainly composed of Fe (iron) fine powder, the weight ratio of Fe fine powder to the total weight of the transition metal fine powder mixture 40 is in the range of 30% to 50%, Transition metal fine powder 39 of one kind of transition metal 38 excluding fine powder (Ti (titanium) fine powder, Cr (chromium) fine powder, Mn (manganese) fine powder, Co (cobalt) fine powder, Ni (nickel) fine powder Transition metal fine powder mixture 40 of at least one of powder, Cu (copper) fine powder, Zn (zinc) fine powder, Nb (niobium) fine powder, Mo (molybdenum) fine powder, and Ag (silver) fine powder And a transition metal fine powder 39 (Ti (titanium) fine powder, Cr (chromium)) of at least one other type of transition metal 38 excluding the fine powder of Fe except for the fine powder of Fe. Fine powder, Mn (manganese Fine powder, Co (cobalt) fine powder, Ni (nickel) fine powder, Cu (copper) fine powder, Zn (zinc) fine powder, Nb (niobium) fine powder, Mo (molybdenum) fine powder, Ag (silver) fine powder The weight ratio of the transition metal fine powder mixture 40 (the other at least one of the bodies) to the total weight is in the range of 3% to 20%.

  As a specific example of the alloy molded product 42 containing Fe (iron) as a main component, a transition metal fine powder mixture 40 in which a fine powder of Fe, a fine powder of Ni, and a fine powder of Cu are uniformly mixed and dispersed is compressed. This is a sintered alloy molded product 42. Further, as a specific example of the alloy fine powder 42 mainly composed of Fe (iron) (alloy fine powder mainly composed of Fe), a fine powder of Fe, a fine powder of Ni, and a fine powder of Cu are uniformly mixed. -The dispersed transition metal fine powder mixture 40 is compressed and then fired to form an alloy molded product 42. The alloy molded product 42 is finely pulverized with a particle size of 10 µm to 200 µm.

  The alloy molded product 42 (alloy fine powder 43) has a weight ratio of Fe fine powder to the total weight of the transition metal fine powder mixture 40 of 48%, and the weight of the Ni fine powder to the total weight of the transition metal fine powder mixture 40. The ratio is 48%, and the weight ratio of the fine powder of Cu to the total weight of the transition metal fine powder mixture 40 is 4%. Since the melting point of Fe is 1536 ° C., the melting point of Ni is 1455 ° C., and the melting point of Cu is 1084.5 ° C., the fine powder of Cu and the fine powder of Ni are melted. To join Fe fine powder.

  As another specific example of the alloy molded product 42 mainly containing Fe (iron), a transition metal fine powder mixture 40 in which fine powder of Fe, fine powder of Ti, and fine powder of Ag are uniformly mixed and dispersed is compressed. An alloy molding 42 fired after firing. Further, as another specific example of the alloy fine powder 43 mainly composed of Fe (alloy fine powder mainly composed of Fe), fine powder of Fe, fine powder of Ti, and fine powder of Ag are mixed uniformly. The dispersed transition metal fine powder mixture 40 is compressed and fired to form an alloy molded product 42. The alloy molded product 42 is finely pulverized with a particle size of 10 μm to 200 μm.

  The alloy molded product 42 (alloy fine powder 43) has a weight ratio of Fe fine powder to the total weight of the transition metal fine powder mixture 40 of 48%, and the weight of the Ti fine powder to the total weight of the transition metal fine powder mixture 40. The ratio is 46%, and the weight ratio of the fine Ag powder to the total weight of the transition metal fine powder mixture 40 is 6%. Since the melting point of Fe is 1536 ° C., the melting point of Ti is 1666 ° C., and the melting point of Ag is 961.93 ° C., the Ag fine powder and the Fe fine powder are melted, and the molten Ag and Fe fine powder serve as a binder. To join the fine powder of Ti.

  As another example of the transition metal fine powder mixture 40, a fine powder of Cu (copper) processed (pulverized) in a powder form is used as a main component, and a fine powder of Cu and a powder excluding Cu are processed (fine pulverized). ) Other transition metals 38 (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Fe (iron), powder Co ( (Cobalt), powdered Ni (nickel), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver)). A transition metal fine powder mixture 40 in which the transition metal fine powder 39 is uniformly mixed and dispersed.

  A transition metal fine-particle mixture 40 obtained by mixing a fine powder of Cu (copper) as a main component and a transition metal fine powder 39 of at least two other types of transition metals 38 excluding Cu has a work function of Cu and excluding Cu. In order to make the work function of the transition metal 38 and the work function of the other at least two kinds of transition metals close to the work function of the platinum group element, at least two other kinds of the transition metals 38 excluding the fine powder of Cu are used. The transition metal fine powder 39 of the transition metal 38 is selected.

  In the alloy molded article 42 containing Cu fine powder as a main component, the transition metal fine powder 39 of at least two kinds of the transition metals 38 among the selected transition metals 38 is melted when the transition metal fine powder mixture 40 is fired, The transition metal fine powder 39 of the transition metal 38 is joined using the molten transition metal fine powder 39 of the transition metal 38 as a binder. The alloy fine powder 43 formed by finely pulverizing the alloy molded product 42 containing Cu as a main component is formed by compressing a transition metal fine powder mixture 40 containing Cu fine powder as a main component and then firing the mixture. The obtained alloy molded product 42 is finely pulverized with a particle size of 10 μm to 200 μm.

  In the transition metal fine powder mixture 40 containing Cu (copper) fine powder as a main component, the weight ratio of the Cu fine powder to the total weight of the transition metal fine powder mixture 40 is in the range of 30% to 50%. Transition metal fine powder 39 of one kind of transition metal 38 excluding fine powder (Ti (titanium) fine powder, Cr (chromium) fine powder, Mn (manganese) fine powder, Fe (iron) fine powder, Co (cobalt) fine powder , Ni (nickel) fine powder, Zn (zinc) fine powder, Nb (niobium) fine powder, Mo (molybdenum) fine powder, and at least one of Ag (silver) fine powder) transition metal fine powder mixture 40 And a transition metal fine powder 39 (Ti (titanium) fine powder, Cr (chromium)) of at least one other type of transition metal 38 excluding Cu fine powder. Fine powder, Mn (manganese Fine powder, Fe (iron) fine powder, Co (cobalt) fine powder, Ni (nickel) fine powder, Zn (zinc) fine powder, Nb (niobium) fine powder, Mo (molybdenum) fine powder, Ag (silver) fine powder The weight ratio of the transition metal fine powder mixture 40 (the other at least one of the bodies) to the total weight is in the range of 3% to 20%.

  As a specific example of the alloy molded product 42 containing Cu (copper) as a main component, a transition metal fine powder mixture 40 obtained by uniformly mixing and dispersing Cu fine powder, Fe fine powder, and Zn fine powder is compressed. This is a sintered alloy molded product 42. Further, as a specific example of the alloy fine powder 43 mainly composed of Cu (copper) (alloy fine powder mainly composed of Cu), a fine powder of Cu, a fine powder of Fe, and a fine powder of Zn are uniformly mixed. -The dispersed transition metal fine powder mixture 40 is compressed and then fired to form an alloy molded product 42. The alloy molded product 42 is finely pulverized with a particle size of 10 µm to 200 µm.

  This alloy molded product 42 (alloy fine powder 43) has a weight ratio of Cu fine powder to the total weight of the transition metal fine powder mixture 40 of 48%, and the weight of the Fe fine powder to the total weight of the transition metal fine powder mixture 40. The ratio was 48%, and the weight ratio of the fine Zn powder to the total weight of the transition metal fine powder mixture 40 was 4%. Since the melting point of Cu is 1084.5 ° C., the melting point of Fe is 1536 ° C., and the melting point of Zn is 419.58 ° C., the fine powder of Zn and the fine powder of Cu are melted. A fine powder of Fe is joined as a binder.

  As another specific example of the alloy molded product 42 containing Cu (copper) as a main component, a transition metal fine powder mixture 40 obtained by uniformly mixing and dispersing Cu fine powder, Fe fine powder, and Ag fine powder is compressed. An alloy molding 42 fired after firing. Further, as another specific example of the alloy fine powder 43 containing Cu as a main component (alloy fine powder containing Cu as a main component), a fine powder of Cu, a fine powder of Fe, and a fine powder of Ag are uniformly mixed. The dispersed transition metal fine powder mixture 40 is compressed and fired to form an alloy molded product 42, and the alloy molded product 42 is finely pulverized with a particle size of 10 μm to 200 μm.

  This alloy molded product 42 (alloy fine powder 43) has a weight ratio of Cu fine powder to the total weight of the transition metal fine powder mixture 40 of 48%, and the weight of the Fe fine powder to the total weight of the transition metal fine powder mixture 40. The ratio is 46%, and the weight ratio of the Ag fine powder to the total weight of the transition metal fine powder mixture 40 is 6%. Since the melting point of Cu is 1084.5 ° C., the melting point of Fe is 1536 ° C., and the melting point of Ag is 961.93 ° C., the Ag fine powder and the Cu fine powder are melted, and the fused Ag and Cu fine powder are melted. The fine powder of Fe is joined as a binder.

  The metal electrode thin plate 27 has a front surface and a rear surface, and has a predetermined area and a thickness of 0.02 to 0.2 mm. The metal electrode thin plate 27 is formed by forming a conductive metal (silver, copper, iron, or a conductive alloy) into a thin plate shape, and has a square shape in plan view. In the metal electrode thin plate 27, a large number of fine channels (fine through holes) through which gas and liquid flow are formed. The planar shape of the metal electrode thin plate 27 is not particularly limited, and may be formed into any other planar shape such as a circle, an ellipse, and a polygon in addition to a square.

  The carbon electrode thin plate 28 has a front surface and a rear surface, has a predetermined area and a thickness of 0.02 to 0.2 mm, and is formed in a quadrangular planar shape. In the carbon electrode thin plate 28, a large number of fine channels (fine through holes) through which gas and liquid flow are formed. The planar shape of the carbon electrode plate 28 is not particularly limited, and may be formed into any other planar shape such as a circle, an ellipse, and a polygon in addition to a square.

  As an example of the carbon electrode thin plate 28, carbon graphite (graphite) powder of several μm to several tens μm and a conductive binder (conductive binder) are formed by cold isostatic pressing and then graphitized at about 3000 ° C. Use a sheet-like electrode material. As another example of the carbon electrode thin plate 28, carbon graphite (graphite) powder of several μm to several tens of μm and a conductive binder (conductive binder) are extruded from an extrusion mold and then graphitized at about 3000 ° C. Use a sheet-like electrode material. As the carbon electrode thin plate 28, glassy carbon can also be used.

  The aggregate 30 of the carbon nanotubes 29 adheres (grows) to both surfaces (front and rear surfaces) of the metal electrode thin plate 27 in which a large number of fine channels (fine through holes) are formed, or a large number of fine channels ( It is fixed (grown) on both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 in which the fine through holes (fine through holes) are formed. As shown in FIG. 6, on the surface of the carbon nanotube 29, the alloy fine particles 26 (alloy fine particles 26 obtained by evaporating the alloy molded product 42) or the alloy fine powder 43 obtained by pulverizing the alloy molded product 42 are formed. The alloy fine particles 26 (alloy fine particles 26 obtained by evaporating the alloy fine powder 43) are carried in a uniformly dispersed state. The carbon nanotubes 29 carrying the alloy fine particles 26 have a large number of fine openings through which gas and liquid flow. The alloy fine particles 26 are supported on the surface of the carbon nanotube 29 by a laser evaporation method. In the polymer electrolyte fuel cell 10 (cell 11), the solid polymer electrolyte membrane 16 and the surface of the carbon nanotube 29 and the alloy fine particles 26 overlap without any gap, and the surface of the solid polymer electrolyte membrane 16 and the carbon nanotube 29 and the alloy fine particles 26 is in close contact with no gap.

  The aggregates 32 of the carbon nanohorns 31 are fixed (grown) on both surfaces (front and rear surfaces) of the metal electrode thin plate 27 in which a large number of fine channels (fine through holes) are formed, or a large number of fine channels ( It is fixed (grown) on both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 in which the fine through holes (fine through holes) are formed. As shown in FIG. 7, on the surface of the carbon nanohorn 31, the alloy fine particles 26 of the alloy molded product 42 (alloy fine particles 26 obtained by evaporating the alloy molded product 42) or the alloy fine powder 43 obtained by pulverizing the alloy molded product 42 are formed. The alloy fine particles 26 (alloy fine particles 26 obtained by evaporating the alloy fine powder 43) are carried in a uniformly dispersed state. The carbon nanohorn 31 carrying the alloy fine particles 26 has a large number of fine openings through which gas and liquid flow. The alloy fine particles 26 are supported on the surface of the carbon nanohorn 31 by a laser evaporation method. In the polymer electrolyte fuel cell 10 (cell 11), the solid polymer electrolyte membrane 16 and the surface of the carbon nanohorn 31 and the alloy fine particles 26 overlap without any gap, and the solid polymer electrolyte membrane 16 and the surface of the carbon nanohorn 31 and the alloy fine particles 26 is in close contact with no gap.

  FIG. 5 is a partially enlarged front view of a carbon nanotube electrode 15A (fuel electrode 13A and air electrode 14A) or a carbon nanohorn electrode 15A (fuel electrode 13A and air electrode 14A) shown as an example, and FIG. It is a conceptual diagram of the carbon nanotube 29 shown as an example carried. FIG. 7 is a conceptual diagram of a carbon nanohorn 31 shown as an example carrying alloy fine particles 26.

  The fuel electrode 13A (carbon nanotube electrode 15A or carbon nanohorn electrode 15A) and the air electrode 14A (carbon nanotube electrode 15A or carbon nanohorn electrode 15A) have a thickness L1 in the range of 0.03 mm to 0.3 mm, preferably 0 mm. It is in the range of 0.05 mm to 0.1 mm. When the thickness L1 of the fuel electrode 13A and the air electrode 14A is less than 0.03 mm, the strength is reduced, and the fuel electrode 13A and the air electrode 14A are easily broken or damaged when an impact is applied, and the shape is maintained. May not be possible. When the thickness L1 of the fuel electrode 13A (the carbon nanotube electrode 15A or the carbon nanohorn electrode 15A) and the air electrode 14A (the carbon nanotube electrode 15A or the carbon nanohorn electrode 15A) exceeds 0.3 mm, the electricity of the fuel electrode 13A and the air electrode 14A is increased. The resistance increases, current does not flow smoothly to the fuel electrode 13A and the air electrode 14A, and when the fuel electrode 13A and the air electrode 15A are used in the polymer electrolyte fuel cell 10, sufficient electricity is generated in the fuel cell 10. Therefore, sufficient electric energy cannot be supplied to the load 37 connected to the fuel cell 10.

  The fuel electrode 13A (carbon nanotube electrode 15A or carbon nanohorn electrode 15A) and the air electrode 14A (carbon nanotube electrode 15A or carbon nanohorn electrode 15A) have a thickness L1 in the range of 0.03 mm to 0.3 mm, preferably 0 mm. Since the fuel electrode 13A and the air electrode 14A are in the range of 0.05 mm to 0.1 mm, the fuel electrode 13A and the air electrode 14A have high strength and can maintain their shapes, and when the impact is applied to the fuel electrode 13A and the air electrode 14A. The fuel electrode 13A and the air electrode 14A can be prevented from being damaged or damaged. Further, by setting the thickness L1 within the above range, the electric resistance of the fuel electrode 13A (carbon nanotube electrode 15A or carbon nanohorn electrode 15A) and the air electrode 14A (carbon nanotube electrode 15A or carbon nanohorn electrode 15A) can be reduced. When the fuel electrode 13A and the air electrode 14A are used in the polymer electrolyte fuel cell 10, sufficient current can be generated in the fuel cell 10 when the fuel electrode 13A and the air electrode 14A flow smoothly. Thus, sufficient electric energy can be supplied to the load 37 connected to the fuel cell 10.

  FIG. 8 is a partially enlarged front view of a carbon nanotube electrode 15B (fuel electrode 13B and air electrode 14B) or a carbon nanohorn electrode 15B (fuel electrode 13B and air electrode 14B) shown as another example, and FIG. FIG. 7 is a conceptual diagram of a carbon nanotube 29 shown as another example carrying 26. FIG. 10 is a conceptual diagram of a carbon nanohorn 31 shown as another example carrying alloy fine particles 26.

  The difference between the carbon nanotube electrode 15B (fuel electrode 13B and air electrode 14B) or the carbon nanohorn electrode 15B (fuel electrode 13B and air electrode 14B) shown in FIG. 8 is different from the electrode 15A (fuel electrode 13A and air electrode 14A) of FIG. The point that the alloy fine particle laminated porous structure 33 is formed on the surface of the carbon nanotube 29 by the alloy fine particles 26 overlapping from the surface of the carbon nanotube 29 to the outside, Since the alloy microporous structure 33 is formed on the surface of the carbon nanohorn 31 and the other configuration is the same as those of the carbon nanotube electrode 15A or the carbon nanohorn electrode 15A of FIG. 5, FIGS. Same as And the description of the electrode 15A (the fuel electrode 13A and the air electrode 14A) in FIGS. 5 to 7 is referred to for a detailed description of the other configuration of the electrode 15B (the fuel electrode 13B and the air electrode 14B). Omitted.

  The fuel electrode 13B (carbon nanotube electrode 15B or carbon nanohorn electrode 15B) and the air electrode 14B (carbon nanotube electrode 15B or carbon nanohorn electrode 15B) have a front surface 24 and a rear surface 25 similar to the fuel electrode 13A and air electrode 14A of FIG. And has a predetermined area and a predetermined thickness dimension L1, and has a square planar shape. The fuel electrode 13B and the air electrode 14B are composed of an alloy fine particle 26 (alloy fine particle) of an alloy molded product 42 (alloy molded product), a metal electrode thin plate 27 or a carbon electrode thin plate 28, and an aggregate 30 of a predetermined area of a carbon nanotube 29 ( (Aggregated plate) or an aggregate 32 (aggregated plate) of carbon nanohorns 31 having a predetermined area.

  The fuel electrode 13B and the air electrode 14B are finely pulverized from the alloy molding 42. The alloy fine particles 26 (alloy fine particles) of the alloy fine powder 43 (alloy fine powder) having a particle size of 10 μm to 200 μm, and the metal electrode thin plate 27 or carbon It may be formed from an electrode thin plate 28 and an aggregate 30 of carbon nanotubes 29 (aggregate plate) of a predetermined area or an aggregate 32 of carbon nanohorns 31 (aggregate plate) of a predetermined area.

  The aggregate 30 of the carbon nanotubes 29 has a thickness of 0.02 to 0.2 mm and is fixed to both surfaces of the metal electrode thin plate 27 in which a large number of fine channels (micropores) are formed. Is 0.02 to 0.2 mm and is fixed to both surfaces of the carbon electrode thin plate 28 in which a large number of fine channels (micropores) are formed. As shown in FIG. 9, on the surface of the carbon nanotube 29, the alloy fine particles 26 of the alloy molded product 42 (the alloy fine particles 26 obtained by evaporating the alloy molded product 42) or the alloy fine powder 43 obtained by pulverizing the alloy molded product 42 are formed. The alloy fine particles 26 (alloy fine particles 26 obtained by evaporating the alloy fine powder 43) are supported, and the alloy fine particles 26 overlapping from the surface of the carbon nanotube 29 to the outside form an alloy fine particle laminated porous structure 33.

  The aggregate 32 of the carbon nanohorns 31 has a thickness of 0.02 to 0.2 mm and is fixed to both surfaces of the metal electrode thin plate 27 in which a large number of fine channels (micropores) are formed. Is 0.02 to 0.2 mm and is fixed to both surfaces of the carbon electrode thin plate 28 in which a large number of fine channels (micropores) are formed. On the surface of the carbon nanohorn 31, as shown in FIG. 10, the alloy fine particles 26 of the alloy molded product 42 (the alloy fine particles 26 obtained by evaporating the alloy molded product 42) or the alloy fine powder 43 obtained by pulverizing the alloy molded product 42 are formed. The alloy fine particles 26 (alloy fine particles 26 obtained by evaporating the alloy fine powder 43) are supported, and the alloy fine particles 26 overlapping from the surface of the carbon nanohorn 31 to the outside form an alloy fine particle laminated porous structure 33.

  The alloy fine powder 26 (alloy fine powder) is made by finely pulverizing an alloy molded product 42 (alloy molded product). The alloy molding 42 compresses a transition metal fine powder mixture 40 obtained by uniformly mixing and dispersing at least three types of transition metal 38 fine powders selected from various transition metal 38 processed into fine powder (fine pulverization). It is made by firing (sintering) after it is done. The transition metal 38, the transition metal fine powder mixture 40, the alloy molded product 42, and the alloy fine powder 43 are the same as those of the fuel electrode 13A and the air electrode 14A in FIG. The particle size of the transition metal fine powder 38, the particle size of the alloy fine powder 43, and the thickness L1 of the fuel electrode 13B and the air electrode 14B are the same as those of the fuel electrode 13A and the air electrode 14A in FIG.

  In the polymer electrolyte fuel cell 10 (cell 11), the solid polymer electrolyte membrane 16 and the surface of the carbon nanotube 29 and the alloy fine particle laminated porous structure 33 overlap without gaps, and the surfaces of the solid polymer electrolyte membrane 16 and the carbon nanotube 29 And the alloy fine particle laminated porous structure 33 is in close contact with no gap. Further, the solid polymer electrolyte membrane 16 and the surface of the carbon nanohorn 31 and the alloy fine particle laminated porous structure 33 overlap without any gap, and the solid polymer electrolyte membrane 16 and the surface of the carbon nanohorn 31 and the alloy fine particle laminated porous structure 33 are tightly spaced. Adhering.

  A large number of fine flow paths 34 (passage holes) having different diameters are formed in the alloy fine particle laminated porous structure 33. A gas (hydrogen gas or oxygen gas) or a liquid (water) flows through these flow paths 34 (passage holes). The flow paths 34 (passage holes) include a plurality of flow openings 35 opening on the front side of the carbon nanotube electrode 15B or the carbon nanohorn electrode 15B and a plurality of flow openings 35 opening on the back side of the electrode 10B. And penetrates the porous alloy layered structure 33 toward the carbon nanotube 29 or the carbon nanohorn 31. These flow paths 34 extend in various directions (thickness direction and vertical and horizontal directions) of the alloy fine particle laminated porous structure 33 while being bent irregularly. These flow paths 34 are partially connected inside the alloy fine particle laminated porous structure 33, and one flow path 34 and the other flow path 34 communicate with each other. The opening areas (opening diameters) of the flow paths 34 (passage holes) are not uniform inside the alloy fine particle laminated porous structure 33 but are irregularly changed.

  The alloy fine particle laminated porous structure 33 has a porosity in the range of 15% to 30% and a relative density in the range of 70% to 85%. If the porosity of the alloy fine particle laminated porous structure 33 is less than 15% and the relative density exceeds 85%, a large number of fine channels 34 (passage holes) are not formed in the alloy fine particle laminated porous structure 33, and the alloy fine particles The specific surface area of the laminated porous structure 33 cannot be increased. If the porosity of the alloy fine particle laminated porous structure 33 exceeds 30% and the relative density is less than 70%, the opening area (opening diameter) of the flow path 34 (passage hole) becomes unnecessarily large, and the alloy fine particle laminated porous structure In some cases, the strength of the alloy particle 33 decreases, and when an impact is applied, the alloy fine particle laminated porous structure 33 is easily broken or damaged, and the form cannot be maintained.

  Since the porosity and the relative density of the alloy fine particle laminated porous structure 33 are in the above ranges, the alloy fine particle laminated porous structure 33 has a large number of fine flow paths 34 (passage holes) having different opening areas (opening diameters). The specific surface area of the alloy fine particle laminated porous structure 33 can be increased, and the gas or liquid flows through the flow path 34 (passage hole) while the gas or liquid flows through the contact surface of the alloy fine particle laminated porous structure 33 (alloy fine particles 26). (The surface of the (alloy fine particles)).

  FIG. 11 is a diagram illustrating power generation by the polymer electrolyte fuel cell 10. FIG. 12 is a diagram illustrating fuel electrodes 13A and 13B (carbon nanotube electrodes 15A and 15B or carbon nanohorn electrodes 15A and 15B) and air electrodes 14A and 14B. It is a figure showing the result of the electromotive force test of (carbon nanotube electrodes 15A and 15B or carbon nanohorn electrodes 15A and 15B). FIG. 13 shows IV characteristics of fuel electrodes 13A and 13B (carbon nanotube electrodes 15A and 15B or carbon nanohorn electrodes 15A and 15B) and air electrodes 13A and 13B (carbon nanotube electrodes 15A and 15B or carbon nanohorn electrodes 15A and 15B). It is a figure showing a result of a test. In the polymer electrolyte fuel cell 10, as shown in FIG. 11, hydrogen (fuel) is supplied to the fuel electrodes 13A and 13B, and air (oxygen) is supplied to the air electrodes 14A and 14B.

At the fuel electrode 13A or 13B, hydrogen is decomposed into protons (hydrogen ions, H ⁺ ) and electrons by a reaction (catalysis) of H ₂ → 2H ⁺ + 2e ⁻ . Thereafter, the protons move through the solid polymer electrolyte membrane 16 to the air electrode 14A or the air electrode 14B, and the electrons move through the conductor 36 to the air electrode 14A or the air electrode 14B. Protons generated at the fuel electrode 13A or the fuel electrode 13B flow through the solid polymer electrolyte membrane 16. At the air electrode 14A or the air electrode 14B, the protons transferred from the solid polymer electrolyte membrane 16 and the electrons transferred on the conductive wire 36 react with oxygen in the air, and water is formed by the reaction of 4H ⁺ + O ₂ + 4e → 2H ₂ O. Generated.

  At least three transition metals are selected from the transition metals such that the work function of the work functions of the at least three transition metals is close to the work function of the platinum group element, and the selected at least three transition metals are selected. The alloy fine particles 26 of the alloy molded product 43 made of are supported on the surface of the carbon nanotube 29 or the carbon nanohorn 31 or the alloy fine particle laminated porous structure 33 is formed on the surface of the carbon nanotube 29 or the carbon nanohorn 31, or the alloy molding The alloy fine particles 26 of the alloy fine powder 43 obtained by pulverizing the product 42 are supported on the surface of the carbon nanotube 29 or the carbon nanohorn 31 or the alloy fine particle laminated porous structure 33 is supported on the surface of the carbon nanotube 29 or the carbon nanohorn 31. 26 or allo The fine particle laminated porous structure 33 constitutes the fuel electrodes 13A and 13B (carbon nanotube electrodes 15A and 15B or carbon nanohorn electrodes 15A and 15B) and the air electrodes 14A and 14B (carbon nanotube electrodes 15A and 15B or carbon nanohorn electrodes 15A and 15B). Therefore, the fuel electrodes 13A and 13B and the air electrodes 14A and 14B exhibit excellent catalytic activity (catalysis), and hydrogen is efficiently decomposed into protons and electrons.

  In the electromotive voltage test, the voltage (V) between the fuel electrode 13A or the fuel electrode 13B and the air electrode 14A or the air electrode 14B (between the electrodes) was measured for 15 minutes after the hydrogen gas was injected. In the diagram showing the results of the electromotive force test in FIG. 12, the horizontal axis represents the measurement time (min), and the vertical axis represents the distance between the fuel electrode 13A or 13B and the air electrode 14A or 14B (between the electrodes). Indicates voltage (V). In a polymer electrolyte fuel cell using a fuel electrode utilizing (supported on) a platinum group element and an air electrode (platinum electrode), as can be seen from the result of the electromotive force test shown in FIG. The voltage with the air electrode was around 1.079 (V). On the other hand, in the polymer electrolyte fuel cell 10 using the fuel electrode 13A (platinum-less electrode) or the fuel electrode 13B (platinum-less electrode) and the air electrode 14A (platinum-less electrode) or the air electrode 14B (platinum-less electrode), The voltage (electromotive force) between the fuel electrode 13A or the fuel electrode 13B and the air electrode 14A or the air electrode 14B (between the electrodes) was 1.04 (V) to 1.03 (V).

  In the IV characteristic test, a load 37 was connected between the fuel electrode 13A or the fuel electrode 13B and the air electrode 14A or the air electrode 14B (between the electrodes), and the relationship between voltage and current was measured. In the diagram showing the results of the IV characteristic test in FIG. 13, the horizontal axis represents current (A) and the vertical axis represents voltage (V). In the polymer electrolyte fuel cell 10 using the fuel electrode 13A (platinum-less electrode) or the fuel electrode 13B (platinum-less electrode) and the air electrode 14A (platinum-less electrode) or the air electrode 14B (platinum-less electrode), FIG. As can be seen from the figure showing the results of the IV characteristic test, the voltage of the polymer electrolyte fuel cell using a fuel electrode (platinum electrode) and an air electrode (platinum electrode) utilizing (supporting) a platinum group element. The result was not much different from the descent rate. As shown in the result of the electromotive force test in FIG. 12 and the result of the IV characteristic test in FIG. 13, the platinum-less fuel electrodes 13A and 13B (carbon nanotube electrodes 15A and 15B or carbon nanohorns) which do not use a platinum group element are used. The electrodes 15A, 15B) and the air electrodes 14A, 14B (carbon nanotube electrodes 15A, 15B or carbon nanohorn electrodes 15A, 15B) have excellent catalytic action to release electrons to promote a reaction to become hydrogen ions, It was confirmed that it had an oxygen reduction function (catalysis) substantially similar to the used fuel electrode and air electrode.

  The polymer electrolyte fuel cell 10 has a carbon nanotube electrode 15A or a carbon nanohorn electrode 15A that is a fuel electrode 13A and an air electrode 14A used therein. The transition metal fine particles of at least three types of transition metals selected from various transition metals. Alloy fine particles 26 (alloy fine particles) of an alloy molded product 42 (or alloy fine powder 43) which is obtained by compressing a transition metal fine powder mixture in which a body is uniformly mixed and dispersed, and a metal electrode thin plate 27 or a carbon electrode thin plate 28; , Formed from the aggregate 30 of the carbon nanotubes 29 or the aggregate 32 of the carbon nanohorns 31 so that the work function of at least three kinds of selected transition metals approximates the work function of the platinum group element, At least three types of transition metals are selected from various types of transition metals, and alloys are selected. Since the particles 26 are supported in a state of being uniformly dispersed on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31, the carbon nanotube electrode 15A having the alloy fine particles 26 supported on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31 ( The fuel electrode 13A and the air electrode 14A) or the carbon nanohorn electrode 15A (the fuel electrode 13A and the air electrode 14A) have substantially the same work function as the fuel electrode and the air electrode containing a platinum group element, and the fuel electrode containing a platinum group element. And can exhibit substantially the same catalytic activity (catalysis) as the air electrode, and generate sufficient electricity in the polymer electrolyte fuel cell 10 using the platinum-less carbon nanotube electrode 15A or carbon nanohorn electrode 15A. And connected to the polymer electrolyte fuel cell 10. It is possible to supply sufficient electric energy to the load 37.

  The alloy fine particles layered porous structure 33 is formed on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31 by the alloy fine particles 26 overlapping from the surface of the carbon nanotube 29 or the carbon nanohorn 31 to the outside, and the solid polymer electrolyte membrane 16 (electrode bonding) is formed. The polymer electrolyte fuel cell 10 in which the body film), the surface of the carbon nanotube 29 or the carbon nanohorn 31 and the alloy fine particle laminated porous structure 33 overlap without any gap, has a structure in which the alloy fine particles are formed on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31. By forming the laminated porous structure 33, the specific surface area of the alloy fine particles 26 can be increased, and the catalytic action of the alloy fine particles 26 can be sufficiently utilized. The carbon nanotube electrode 15B (the fuel electrode 13B and the air electrode 14B) or the carbon nanohorn electrode 15B (the fuel electrode 13B and the air electrode 14B) has substantially the same work function as the fuel electrode and the air electrode containing a platinum group element. Can exhibit substantially the same catalytic activity (catalysis) as a fuel electrode containing a group III element and an air electrode, and can be sufficiently used in a polymer electrolyte fuel cell 10 using a platinum-less carbon nanotube electrode 15B or a carbon nanohorn electrode 15B. Power can be generated, and sufficient electric energy can be supplied to the load 37 connected to the polymer electrolyte fuel cell 10.

  The polymer electrolyte fuel cell 10 has a carbon nanotube electrode 15A, 15B (fuel electrode 13A, 13B and air electrode 14A, 14B) or a carbon nanohorn electrode 15A, 15B (fuel electrode 13A, 13B and air electrode 14A, 14B) uses alloy fine particles 26 (alloy molding 42) made from transition metal fine powders of at least three types of transition metals selected from various transition metals, and does not use expensive platinum group elements. And the polymer electrolyte fuel cell 10 can be manufactured at low cost.

  The polymer electrolyte fuel cell 10 in which the transition metal fine powder mixture is mainly composed of Ni (nickel) fine powder has a combined work of the work function of Ni and the work function of at least two types of transition metals other than Ni. Since at least two types of fine powders of transition metals other than the fine powder of Ni are selected from various transition metals so that the function is close to the work function of the platinum group element, the surface of the carbon nanotube 29 is selected. Alternatively, carbon nanotube electrodes 15A, 15B (fuel electrodes 13A, 13B and air electrodes 14A, 14B) or carbon nanohorn electrodes 15A, 15B (fuel electrodes 13A, 13B and the cathodes 14A, 14B) have substantially the same work functions as the anode and cathode containing the platinum group element. It is capable of exhibiting substantially the same catalytic activity (catalysis) as a fuel electrode and an air electrode containing a platinum group element, and is a solid polymer type using platinum-less carbon nanotube electrodes 15A, 15B or carbon nanohorn electrodes 15A, 15B. Sufficient electricity can be generated in the fuel cell 10 and sufficient electric energy can be supplied to the load connected to the polymer electrolyte fuel cell 10.

  The polymer electrolyte fuel cell 10 in which the transition metal fine powder mixture is mainly composed of fine powder of Fe (iron) is a composite work of the work function of Fe and the work function of at least two types of transition metals other than Fe. Since at least two types of fine powders of transition metals other than the fine powder of Fe are selected from various transition metals so that the function is close to the work function of the platinum group element, the surface of the carbon nanotube 29 is selected. Alternatively, the carbon nanotube electrodes 15A and 15B (the fuel electrodes 13A and 13B and the air electrodes 14A and 14B) or the carbon nanohorn electrodes 15A and 15B (the fuel electrodes 13A and 13B) having the alloy fine particles 26 or the alloy fine particle laminated porous structure 33 on the surface of the carbon nanohorn 31. 13B and the cathodes 14A and 14B) have substantially the same work function as the fuel electrode and the cathode including the platinum group element. A polymer electrolyte fuel cell capable of exhibiting substantially the same catalytic activity (catalysis) as a fuel electrode and an air electrode containing an element and using platinum-free carbon nanotube electrodes 15A and 15B or carbon nanohorn electrodes 15A and 15B. In 10, sufficient electricity can be generated, and sufficient electric energy can be supplied to the load connected to the polymer electrolyte fuel cell 10.

  The polymer electrolyte fuel cell 10 in which the transition metal fine powder mixture is mainly composed of Cu (copper) fine powder has a composite work of a work function of Cu and a work function of at least two types of transition metals other than Cu. Since at least two types of transition metal fine powder excluding Cu fine powder are selected from various transition metals so that the function approximates the work function of the platinum group element, the surface of the carbon nanotube 29 is Alternatively, carbon nanotube electrodes 15A, 15B (fuel electrodes 13A, 13B and air electrodes 14A, 14B) or carbon nanohorn electrodes 15A, 15B (fuel electrodes 13A, 13B and the cathodes 14A and 14B) have substantially the same work function as the fuel electrode and the cathode including the platinum group element. A polymer electrolyte fuel cell capable of exhibiting substantially the same catalytic activity (catalysis) as a fuel electrode and an air electrode containing an element and using platinum-free carbon nanotube electrodes 15A and 15B or carbon nanohorn electrodes 15A and 15B. In 10, sufficient electricity can be generated, and sufficient electric energy can be supplied to the load connected to the polymer electrolyte fuel cell 10.

  FIG. 14 is a diagram illustrating a method of manufacturing the carbon nanotube electrodes 15A and 15B or the carbon nanohorn electrodes 15A and 15B. As shown in FIG. 14, the electrodes 15A and 15B are provided with a transition metal selection step S1, a transition metal fine powder mixture preparation step S2, a transition metal fine powder compressed substance preparation step S3, an alloy molded article preparation step S4, and an alloy particle support step S5. It is manufactured by an electrode manufacturing method having the following. Note that an alloy fine powder preparation step S6 may be performed between the alloy molded product preparation step S4 and the alloy fine particle supporting step S5.

  In the transition metal selection step S1, the various transition metals 38 are selected from various transition metals 38 so that the composite work function of the work functions of at least three types of transition metals 38 selected from the various transition metals 38 approximates the work function of the platinum group element. At least three types of transition metals 38 (Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Nb ( Niobium), Mo (molybdenum), Ag (silver)).

  In the transition metal selection step S1, as described above, in the transition metal fine powder mixture 40 (alloy fine particles 26 and the alloy fine particle laminated porous structure 33) mainly containing Ni (nickel), Cu (copper) and ZN (zinc) are used. ) Or Mn (manganese) and Mo (molybdenum). In the transition metal fine powder mixture 40 (alloy fine particles 26 and alloy fine particle laminated porous structure 33) mainly containing Fe (iron), Ni (nickel) and Cu (copper) are selected, or Ti (titanium) and Ag are used. Select (Silver). In the transition metal fine powder mixture 49 (alloy fine particles 26 and the alloy fine particle laminated porous structure 33) mainly containing Cu (copper), Fe (iron) and Zn (zinc) are selected, or Fe (iron) and Ag are used. Select (Silver).

  In the transition metal fine powder mixture preparation step S2, a transition metal fine powder mixture 40 is prepared by uniformly mixing and dispersing transition metal fine powders 39 of at least three types of transition metals 38 selected in the transition metal selection step S1. In the transition metal fine powder mixture preparing step S2, in the transition metal fine powder mixture 40 (alloy fine particles 26 and the alloy fine particle laminated porous structure 33) containing Ni (nickel) as a main component, Ni, Ni selected in the transition metal selecting step S1 is selected. Each of Cu (copper) and ZN (zinc) is finely pulverized to a particle size of 10 μm to 200 μm by a fine pulverizer to prepare a Ni fine powder 39, a Cu fine powder 39, and a Zn fine powder 39. Next, the Ni fine powder 39, the Cu fine powder 39, and the Zn fine powder 39 are put into a mixer, and the Ni fine powder 39, the Cu fine powder 39, and the Zn fine powder 39 are stirred by the mixer. The mixture is mixed to prepare a transition metal fine powder mixture 40 in which the Ni fine powder 39, the Cu fine powder 39, and the Zn fine powder 39 are uniformly mixed and dispersed.

  Alternatively, each of Ni (nickel), Mn (manganese), and Mo (molybdenum) selected in the transition metal selection step S1 is finely pulverized to a particle diameter of 10 μm to 200 μm by a fine pulverizer to obtain a fine Ni powder 39, Mn. And a Mo fine powder 39 are prepared. Next, the Ni fine powder 39, the Mn fine powder 39, and the Mo fine powder 39 are put into a mixer, and the Ni fine powder 39, the Mn fine powder 39, and the Mo fine powder 39 are stirred by the mixer. The transition metal fine powder mixture 40 in which the Ni fine powder 39, the Mn fine powder 39, and the Mo fine powder 39 are mixed and dispersed uniformly is prepared.

  In the transition metal fine powder mixture preparing step S2, in the transition metal fine powder mixture 40 (alloy fine particles 26 and the alloy fine particle laminated porous structure 33) containing Fe (iron) as a main component, Fe, Each of Ni (nickel) and Cu (copper) is finely pulverized to a particle size of 10 μm to 200 μm by a fine pulverizer to prepare Fe fine powder 39, Ni fine powder 39, and Cu fine powder 39. Next, the fine powder 39 of Fe, the fine powder 39 of Ni, and the fine powder 39 of Cu are charged into a mixer, and the fine powder 39 of Fe, the fine powder 39 of Ni, and the fine powder 39 of Cu are stirred by the mixer. The mixture is mixed to form a transition metal fine powder mixture 40 in which the fine powder 39 of Fe, the fine powder 39 of Ni, and the fine powder 39 of Cu are uniformly mixed and dispersed.

  Alternatively, each of Fe (iron), Ti (titanium), and Ag (silver) selected in the transition metal selection step S1 is finely pulverized to a particle size of 10 μm to 200 μm by a fine pulverizer, and the fine powder of Fe 39, Ti Of fine powder 39 of Ag and fine powder 39 of Ag. Next, the fine powder 39 of Fe, the fine powder 39 of Ti, and the fine powder 39 of Ag are charged into a mixer, and the fine powder 39 of Fe, the fine powder 39 of Ti, and the fine powder 39 of Ag are stirred by the mixer. The mixture is mixed to form a transition metal fine powder mixture 40 in which the fine powder 39 of Fe, the fine powder 39 of Ti, and the fine powder 39 of Ag are uniformly mixed and dispersed.

  In the transition metal fine powder mixture preparation step S2, in the transition metal fine powder mixture 40 (alloy fine particles 26 and the alloy fine particle laminated porous structure 33) containing Cu (copper) as a main component, the Cu selected in the transition metal selection step S1 Each of Fe (iron) and Zn (zinc) is finely pulverized by a fine pulverizer to a particle size of 10 μm to 200 μm to prepare a fine powder 39 of Cu, a fine powder 39 of Fe, and a fine powder 39 of Zn. Next, the Cu fine powder 39, the Fe fine powder 39, and the Zn fine powder 39 are put into a mixer, and the Cu fine powder 39, the Fe fine powder 39, and the Zn fine powder 39 are stirred by the mixer. The mixture is mixed to form a transition metal fine powder mixture 40 in which the Cu fine powder 39, the Fe fine powder 39, and the Zn fine powder 39 are uniformly mixed and dispersed.

  Alternatively, each of Cu (copper), Fe (iron), and Ag (silver) selected in the transition metal selection step S1 is finely pulverized to a particle diameter of 10 μm to 200 μm by a fine pulverizer, and the Cu fine powder 39, Fe Of fine powder 39 and Ag fine powder 39 are prepared. Next, the Cu fine powder 39, the Fe fine powder 39, and the Ag fine powder 39 are put into a mixer, and the Cu fine powder 39, the Fe fine powder 39, and the Ag fine powder 39 are stirred by the mixer. The mixture is mixed to form a transition metal fine powder mixture 40 in which the Cu fine powder 39, the Fe fine powder 39, and the Ag fine powder 39 are uniformly mixed and dispersed.

  In the transition metal fine powder compressed material producing step S3, the transition metal fine powder mixture 40 produced in the transition metal fine powder mixture producing step S2 is pressurized at a predetermined pressure to compress the transition metal fine powder mixture 40 into a predetermined area and a predetermined thickness. To produce a compressed transition metal fine powder 41. In the transition metal fine powder compact creation step S3, the transition metal fine powder mixture 40 is put into a predetermined mold, and the transition metal fine powder compact 41 is produced by press working in which the mold is pressed (pressed) by a press machine. The press pressure (pressure) during the press working is in the range of 500 MPa to 800 MPa.

  If the pressing pressure (pressure) is less than 500 MPa, the transition metal fine powder mixture 40 cannot be sufficiently compressed, and the transition metal fine powder compressed product 41 having a predetermined area and a predetermined thickness cannot be produced. If the pressing pressure (pressure) exceeds 800 MPa, the hardness of the alloy molded product 42 produced in the alloy molded product making step S4 becomes unnecessarily high, and the alloy molded product 42 is smoothly evaporated in the alloy fine particle supporting step S5. Therefore, the alloy fine powder 43 having a desired particle size cannot be produced in the alloy fine powder producing step S6. In the electrode manufacturing method, the transition metal fine powder mixture 41 is pressurized (compressed) at a pressure in the above range, whereby a transition metal fine powder compression product 41 having a predetermined hardness can be produced. Is fired to form an alloy molded product 42 having a predetermined hardness, the alloy molded product 42 can be smoothly evaporated, and the alloy molded product 42 is finely pulverized to form an alloy fine powder 43 having a predetermined particle size. Can be.

  In the transition metal fine powder compact creation step S3, in the transition metal fine powder mixture 40 containing Ni (nickel) as a main component, Ni fine powder 39, Cu (copper) fine powder 39, ZN (zinc) fine powder 39 A predetermined amount of the transition metal fine powder mixture 40 obtained by mixing the transition metal fine powder mixture 40 is charged into a mold, and the transition metal fine powder mixture 40 is pressed by press working to compress the transition metal fine powder mixture 40 and have a predetermined area and a predetermined thickness of the transition metal. A compressed fine powder 41 is produced. Alternatively, a predetermined amount of a transition metal fine powder mixture 40 obtained by mixing Ni fine powder 39, Mn (manganese) fine powder 39, and Mo (molybdenum) fine powder 39 is charged into a mold, and the transition metal fine powder mixture is added. The transition metal fine powder mixture 40 is compressed by pressing to form a transition metal fine powder mixture 41 having a predetermined area and a predetermined thickness.

  In the transition metal fine powder compact creation step S3, in the transition metal fine powder mixture 40 mainly containing Fe (iron), the fine powder 39 of Fe, the fine powder 39 of Ni (nickel), and the fine powder of Cu (copper) are used. A predetermined amount of the transition metal fine powder mixture 40 into which the mixture 39 is mixed is charged into a mold, and the transition metal fine powder mixture 40 is pressed by press working to compress the transition metal fine powder mixture 40 into a predetermined area and a predetermined thickness. The compressed metal fine powder 41 is produced. Alternatively, a predetermined amount of a transition metal fine powder mixture 40 obtained by mixing Fe fine powder 39, Ti (titanium) fine powder 39, and Ag (silver) fine powder 39 is charged into a mold, and the transition metal fine powder mixture is added. The transition metal fine-powder mixture 40 is compressed by pressing to form a transition metal fine-powder mixture 41 having a predetermined area and a predetermined thickness.

  In the transition metal fine powder compact creation step S3, in the transition metal fine powder mixture 40 containing Cu (copper) as a main component, Cu fine powder 39, Fe (iron) fine powder 39, Zn (zinc) fine powder A predetermined amount of the transition metal fine powder mixture 40 into which the mixture 39 is mixed is put into a mold, and the transition metal fine powder mixture 40 is pressed (compressed) by press working to compress the transition metal fine powder mixture 40 into a predetermined area. A transition metal fine powder compact 41 having a predetermined thickness is produced. Alternatively, a predetermined amount of a transition metal fine powder mixture 40 obtained by mixing Cu fine powder 39, Fe (iron) fine powder 39, and Ag (silver) fine powder 39 is charged into a mold, and the transition metal fine powder mixture is added. The transition metal fine-powder mixture 40 is compressed by pressing to form a transition metal fine-powder mixture 41 having a predetermined area and a predetermined thickness.

  In the alloy molded product creation step S4, the transition metal fine powder compact 41 created in the transition metal fine powder compact creation step S3 is charged into a furnace (a steam superheater, an electric furnace, or the like), and the transition metal fine powder compact 41 is placed. Is fired (sintered) at a predetermined temperature in a furnace to produce an alloy molded article 42 having a porous structure in which a number of fine channels (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. In the alloy molded product preparation step S4, the transition metal fine powder compact 41 is fired for a long time at a temperature at which at least two types of the transition metals 38 among the at least three types of transition metals 38 selected in the transition metal selection step S1 are melted. . The firing (sintering) time is 3 hours to 6 hours. In the alloy molded article forming step S4, at the time of firing the compressed transition metal fine powder 41 compressed to a predetermined area and a predetermined thickness, the fine powder 39 of at least two types of transition metals 38 is melted, and the molten transition metal 38 is melted. The fine powder 39 of another transition metal 38 is joined (fixed) using the fine powder 39 as a binder.

  In the alloy molded article preparation step S4, in the transition metal fine powder compact 41 mainly composed of Ni (nickel), Ni fine powder 39, Cu (copper) fine powder 39, and ZN (zinc) fine powder 39 are mixed. The compressed transition metal fine powder mixture 41 obtained by compressing the transition metal fine powder mixture 40 is fired in a furnace for a long time to form a porous structure having a large number of fine channels (passage holes) having an opening diameter in a range of 1 μm to 100 μm. An alloy molding 42 is made. In the alloy molded article 42 formed from the Ni fine powder 39, the Cu fine powder 39, and the Zn fine powder 39, the transition metal is formed at a temperature at which the Zn and Cu fine powder 39 is melted (for example, 1100 ° C to 1200 ° C). The compressed fine powder 41 is fired (sintered), and the Ni fine powder 39 is joined (fixed) by the molten Zn and Cu fine powder 39.

  Further, in the alloy molded article preparation step S4, the transition metal fine powder compact 41 mainly composed of Ni (nickel) contains Ni fine powder 39, Mn (manganese) fine powder 39, and Mo (molybdenum) fine powder. The compressed transition metal fine powder mixture 41 obtained by compressing the transition metal fine powder mixture 40 mixed with 39 was fired in a furnace for a long time to form a large number of fine channels (passage holes) having an opening diameter in the range of 1 μm to 100 μm. An alloy molded article 42 having a porous structure is produced. In the alloy molded article 42 formed from the Ni fine powder 39, the Mn fine powder 39, and the Mo fine powder 39, the transition metal is heated at a temperature at which the Mn and Ni fine powder 39 are melted (for example, 1460 ° C to 1500 ° C). The compressed fine powder 41 is baked, and the Mo fine powder 39 is joined (fixed) by the molten Mn and Ni fine powder 39.

  In the alloy molded article preparation step S4, in the transition metal fine powder compact 41 mainly containing Fe (iron), the fine powder 39 of Fe, the fine powder 39 of Ni (nickel), and the fine powder 39 of Cu (copper) are mixed. A porous structure in which the compressed transition metal fine powder mixture 41 obtained by compressing the mixed transition metal fine powder mixture 40 is fired in a furnace for a long time to form a large number of fine channels (passage holes) having an opening diameter in the range of 1 μm to 100 μm. Is made. In the alloy molded article 42 formed from the fine powder 39 of Fe, the fine powder 39 of Ni, and the fine powder 39 of Cu, the transition metal is heated at a temperature at which the fine powder 39 of Cu and Ni is melted (for example, 1460 ° C to 1500 ° C). The fine powder compact 41 is baked, and the Fe fine powder 39 is joined (fixed) by the molten Cu and Ni fine powder 39.

  Further, in the alloy molded article preparation step S4, the transition metal fine powder compact 41 containing Fe (iron) as a main component has a fine powder 39 of Fe, a fine powder 39 of Ti (titanium), and a fine powder of Ag (silver). The compressed transition metal fine powder mixture 41 obtained by compressing the transition metal fine powder mixture 40 mixed with 39 was fired in a furnace for a long time to form a large number of fine channels (passage holes) having an opening diameter in the range of 1 μm to 100 μm. An alloy molded article 42 having a porous structure is produced. In the alloy molded article 42 formed from the fine powder 39 of Fe, the fine powder 39 of Ti, and the fine powder 39 of Ag, the transition metal is formed at a temperature at which the fine powder 39 of Ag and Fe is melted (for example, 1540 ° C. to 1600 ° C.). The compressed fine powder 41 is baked, and the Ti fine powder 39 is joined (fixed) by the molten Ag and Fe fine powder 39.

  In the alloy molded article preparation step S4, the transition metal fine powder compact 41 containing Cu (copper) as a main component is composed of Cu fine powder 39, Fe (iron) fine powder 39, and Zn (zinc) fine powder 39. A porous structure in which the compressed transition metal fine powder mixture 41 obtained by compressing the mixed transition metal fine powder mixture 40 is fired in a furnace for a long time to form a large number of fine channels (passage holes) having an opening diameter in the range of 1 μm to 100 μm. Is made. In the alloy molded article 42 formed from the Cu fine powder 39, the Fe fine powder 39, and the Zn fine powder 39, the transition metal is formed at a temperature at which the Zn and Cu fine powder 39 is melted (for example, 1090 ° C. to 1200 ° C.). The compressed fine powder 41 is baked, and the fine powder 39 of Fe is joined (fixed) by the fine powder 39 of Zn and Cu melted.

  Further, in the alloy molded article preparation step S4, the transition metal fine powder compact 41 containing Cu (copper) as a main component includes the Cu fine powder 39, the Fe (iron) fine powder 39, and the Ag (silver) fine powder. The compressed transition metal fine powder mixture 41 obtained by compressing the transition metal fine powder mixture 40 mixed with 39 was fired in a furnace for a long time to form a large number of fine channels (passage holes) having an opening diameter in the range of 1 μm to 100 μm. An alloy molded article 42 having a porous structure is produced. In the alloy molded article 42 formed from the Cu fine powder 39, the Fe fine powder 39, and the Ag fine powder 39, the transition metal is formed at a temperature at which the Ag and Cu fine powder 39 are melted (for example, 1090 ° C. to 1200 ° C.). The fine powder compact 41 is baked, and the Fe fine powder 39 is joined (fixed) by the molten Ag and Cu fine powder 39.

  In the alloy fine particle supporting step S5, the alloy molded article 42 produced in the alloy molded article forming step S4 is evaporated by a laser evaporation method, and the alloy fine particles 26 of the alloy molded article 42 are deposited on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31. Carry it. The alloy fine particles 26 are carried on the surface of the carbon nanotubes 29 in a state of being uniformly dispersed on the surface of the carbon nanotubes 29, and are carried on the surface of the carbon nanohorns 31 in a state of being uniformly dispersed on the surface of the carbon nanohorns 31. By carrying the alloy fine particles 26 on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31, the carbon nanotube electrode 15A or the carbon nanohorn electrode 15A is produced. In the alloy fine particle supporting step S5, the carbon nanotube electrode 15A or the carbon nanohorn electrode 15A is formed into a thickness L1 in the range of 0.03 mm to 0.3 mm.

  As a method for supporting the alloy fine particles 26, carbon nanotubes 29 or carbon nanohorns 31 were formed (grown) on both surfaces (front and rear surfaces) of the metal electrode thin plate 27 or both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 by a laser evaporation method. Thereafter, the alloy molded product 26 is evaporated by a laser evaporation method, and the alloy fine particles 26 of the alloy molded product 42 are supported on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31, or on both surfaces (front and rear surfaces) of the metal electrode thin plate 27. ) Or when carbon nanotubes 29 or carbon nanohorns 31 are formed (grown) on both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 by laser evaporation, the alloy molded article 42 is evaporated by laser evaporation, Surface or carbon nanohorn A first surface which may be carrying the alloy particles 26 of alloy molded product 42.

  Further, in the alloy fine particle supporting step S5, the alloy molded article 42 produced in the alloy molded article forming step is evaporated by a laser evaporation method, and the alloy fine particles 26 of the alloy molded article 42 are formed on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31. And the alloy fine particles 26 overlapping outward from the surface of the carbon nanotube 29 or the carbon nanohorn 31 to form an alloy fine particle laminated porous structure 33. The alloy fine particles 26 are supported on the surface of the carbon nanotubes 29 in a state of being uniformly dispersed on the surface of the carbon nanotubes 29 and overlap, and are supported on the surface of the carbon nanohorns 31 in a state of being uniformly dispersed on the surface of the carbon nanohorns 31 and overlap. Thus, an alloy fine particle laminated porous structure 33 is formed. The carbon nanotube electrode 15B or the carbon nanohorn electrode 15B is formed by forming an alloy fine particle laminated porous structure 33 composed of a large number of alloy fine particles 26 on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31. In the alloy particle supporting step S5 for forming the alloy particle laminated porous structure 33, the carbon nanotube electrode 15B or the carbon nanohorn electrode 15B is formed to have a thickness L1 in the range of 0.03 mm to 0.3 mm.

  As a method for forming the alloy fine particle laminated porous structure 33, the carbon nanotubes 29 or the carbon nanohorns 31 are formed on both surfaces (front and rear surfaces) of the metal electrode thin plate 27 or both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 by a laser evaporation method ( Thereafter, the alloy molded product 42 is evaporated by a laser evaporation method, and the alloy fine particles 26 of the alloy molded product 42 are supported on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31 to form an alloy fine particle laminated porous structure 33. Or when the carbon nanotubes 29 or the carbon nanohorns 31 are formed (grown) on both surfaces (front and rear surfaces) of the metal electrode thin plate 27 or both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 by laser evaporation, and at the same time, laser evaporation is performed. Alloy molding 42 products by the method Emitted thereby, in some cases by supporting the alloy particles 26 of alloy molded product 42 on the surface of the surface or a carbon nanohorn 31 of carbon nanotubes 29 forming an alloy particle laminated porous structure 33.

  When the alloy fine powder making step S6 is performed between the alloy molded article making step S4 and the alloy fine particle supporting step S5, in the alloy fine powder making step S6, the alloy molded article made in the alloy molded article making step S4 42 is finely pulverized to a particle size of 10 μm to 200 μm by a fine pulverizer to produce an alloy fine powder 43. As an example of an alloy fine powder 43 containing Ni (nickel) as a main component (an alloy fine powder containing Ni as a main component), Ni fine powder 39, Cu fine powder 39, and ZN fine powder 39 are uniformly mixed. A compressed transition metal fine powder mixture 41 obtained by compressing the dispersed transition metal fine powder mixture 40 is fired to form an alloy molded product 42, and the alloy molded product 42 is finely pulverized by a pulverizer to a particle size of 10 μm to 200 μm. It is finely pulverized. Another example of the alloy fine powder 43 mainly composed of Ni (nickel) is a transition metal fine powder mixture 40 in which Ni fine powder 39, Mn fine powder 39, and Mo fine powder 39 are uniformly mixed and dispersed. This is a finely pulverized product obtained by firing a compressed transition metal fine powder 41, which is obtained by compressing the above, into an alloy molded product 42, and finely pulverizing the alloy molded product 42 to a particle size of 10 μm to 200 μm by a fine pulverizer.

  As an example of the alloy fine powder 43 containing Fe (iron) as a main component (alloy fine powder containing Fe as a main component), a fine powder 39 of Fe, a fine powder 39 of Ni, and a fine powder 39 of Cu are uniformly mixed. A compressed transition metal fine powder mixture 41 obtained by compressing the dispersed transition metal fine powder mixture 40 is fired to form an alloy molded product 42, and the alloy molded product 42 is finely pulverized by a pulverizer to a particle size of 10 μm to 200 μm. It is finely pulverized. Another example of the alloy fine powder 43 containing Fe (iron) as a main component is a transition metal fine powder mixture 40 obtained by uniformly mixing and dispersing a fine powder 39 of Fe, a fine powder 39 of Ti, and a fine powder 39 of Ag. This is a finely pulverized product obtained by firing a compressed transition metal fine powder 41, which is obtained by compressing the above, into an alloy molded product 42, and finely pulverizing the alloy molded product 42 to a particle size of 10 μm to 200 μm by a fine pulverizer.

  As an example of the alloy fine powder 43 mainly composed of Cu (copper) (alloy fine powder mainly composed of Cu), a fine powder 39 of Cu, a fine powder 39 of Fe, and a fine powder 39 of Zn are uniformly mixed. A compressed transition metal fine powder mixture 41 obtained by compressing the dispersed transition metal fine powder mixture 40 is fired to form an alloy molded product 42, and the alloy molded product 42 is finely pulverized by a pulverizer to a particle size of 10 μm to 200 μm. It is finely pulverized. Another example of the alloy fine powder 43 containing Cu (copper) as a main component is a transition metal fine powder mixture 40 in which Cu fine powder 39, Fe fine powder 39, and Ag fine powder 39 are uniformly mixed and dispersed. This is a finely pulverized product obtained by firing a compressed transition metal fine powder 41, which is obtained by compressing the above, into an alloy molded product 42, and finely pulverizing the alloy molded product 42 to a particle size of 10 μm to 200 μm by a fine pulverizer.

  In the alloy fine particle supporting step S5 performed after the alloy fine powder forming step S6, the alloy fine powder 43 formed in the alloy fine powder forming step S6 is evaporated by a laser evaporation method, and the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31 is formed. The alloy fine particles 43 of the alloy fine powder 43 are supported on the substrate. The alloy fine particles 26 are carried on the surface of the carbon nanotubes 29 in a state of being uniformly dispersed on the surface of the carbon nanotubes 29, and are carried on the surface of the carbon nanohorns 31 in a state of being uniformly dispersed on the surface of the carbon nanohorns 31. By carrying the alloy fine particles 43 on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31, the carbon nanotube electrode 15B or the carbon nanohorn electrode 15B is produced. In the alloy fine particle supporting step S5, the carbon nanotube electrode 15B or the carbon nanohorn electrode 15B is formed into a thickness L1 in the range of 0.03 mm to 0.3 mm.

  As a method for supporting the alloy fine particles 26, carbon nanotubes 29 or carbon nanohorns 31 were formed (grown) on both surfaces (front and rear surfaces) of the metal electrode thin plate 27 or both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 by a laser evaporation method. Thereafter, the alloy fine powder 43 is evaporated by a laser evaporation method, and the alloy fine powder 26 of the alloy fine powder 43 is carried on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31, or on both surfaces (front and rear surfaces) of the metal electrode thin plate 27. ) Or when the carbon nanotubes 29 or carbon nanohorns 31 are formed (grown) on both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 by the laser evaporation method, and at the same time, the alloy fine powder 43 is evaporated by the laser evaporation method. Surface or carbon nanohorn A first surface which may be carrying the alloy particles 26 of the alloy fine powder 43.

  In the alloy fine powder supporting step S5, the alloy fine powder 43 produced in the alloy fine powder forming step S6 is evaporated by a laser evaporation method, and the alloy fine powder 43 of the alloy fine powder 43 is formed on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31. The alloy fine particle layered porous structure 33 is formed by the alloy fine particles 26 superposed outward from the surface of the carbon nanotube 29 or the carbon nanohorn 31 while supporting the carbon nano tube 26. The alloy fine particles 26 are supported on the surface of the carbon nanotubes 29 in a state of being uniformly dispersed on the surface of the carbon nanotubes 29 and overlap, and are supported on the surface of the carbon nanohorns 31 in a state of being uniformly dispersed on the surface of the carbon nanohorns 31 and overlap. Thus, an alloy fine particle laminated porous structure 33 is formed. The carbon nanotube electrode 15B or the carbon nanohorn electrode 15B is formed by forming an alloy fine particle laminated porous structure 33 composed of a large number of alloy fine particles 26 on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31. In the alloy particle supporting step S5 for forming the alloy particle laminated porous structure 33, the carbon nanotube electrode 15B or the carbon nanohorn electrode 15B is formed to have a thickness L1 in the range of 0.03 mm to 0.3 mm.

  As a method of forming the alloy fine particle laminated porous structure, carbon nanotubes 29 or carbon nanohorns 31 are generated (grown) on both surfaces (front and rear surfaces) of the metal electrode thin plate 27 or both surfaces (front and rear surfaces) of the carbon electrode thin plate 28 by laser evaporation. After that, the alloy fine powder 43 is evaporated by a laser evaporation method, and the alloy fine particles 26 of the alloy fine powder 43 are supported on the surface of the carbon nanotube 29 or the surface of the carbon nanohorn 31 to form an alloy fine particle laminated porous structure 33. When the carbon nanotubes 29 or the carbon nanohorns 31 are generated (grown) on both sides (front and back surfaces) of the metal electrode thin plate 27 or both surfaces (front and back surfaces) of the carbon electrode thin plate 31 by laser evaporation, the laser evaporation method is used. Alloy fine powder 43 is evaporated by So, there is a case of forming the alloy particle laminated porous structure 33 by supporting the alloy particles 26 of the alloy fine powder 43 to the surface or surfaces of the carbon nanohorn 31 of carbon nanotubes 29.

  The electrode manufacturing method includes at least three of the various transition metals 38 such that the composite work function of the work functions of the at least three types of transition metals 38 selected from the various transition metals 38 approximates the work function of the platinum group element. Transition metal selection step S1 for selecting one kind of transition metal 38, and transition metal fine powder mixture 40 obtained by uniformly mixing and dispersing transition metal fine powder 39 of at least three types of transition metals 38 selected in transition metal selection step S1. Transition metal fine powder mixture forming step S2, and the transition metal fine powder mixture 40 formed by the transition metal fine powder mixture forming step S2 are pressurized at a predetermined pressure to form a transition metal fine powder compressed product 41. The compacted transition metal fine powder 41 produced in the compacted material preparation step S3 and the transition metal fine powder compacted step S3 is fired at a predetermined temperature to form an alloy. An alloy molded article producing step S4 for producing the carbon nanotube 29 or the carbon nanohorn 31 is generated, and the alloy molded article 43 produced in the alloy molded article producing step S4 is evaporated to form the surface of the carbon nanotube 29 or the carbon nanohorn 31. Since the carbon nanotube electrodes 15A and 15B or the carbon nanohorn electrodes 15A and 15B can be formed by the alloy fine particle supporting step S5 of supporting the alloy fine particles 26 of the alloy molded product 43 on the surface, platinum that does not use a platinum group element is used. Electrodes 15A and 15B can be manufactured at low cost, the catalyst function can be used sufficiently and reliably, and it has excellent catalytic activity (catalysis) and is suitable for the polymer electrolyte fuel cell 10. Inexpensive platinum-free electrodes 15A and 15B that can be used for It can be made.

  In the electrode manufacturing method, carbon nanotubes 29 or carbon nanohorns 31 are fixed to both surfaces (front and rear surfaces) of the metal electrode thin plate 27 or both surfaces (front and rear surfaces) of the carbon electrode thin plate 28, and alloy fine particles are attached to the surface of the carbon nanotube 29 or carbon nanohorn 31. 26 or a carbon nanotube electrode 15A, 15B or carbon nanohorn electrode 15A having a thickness L1 of 0.03 mm to 0.3 mm in which an alloy fine particle laminated porous structure 33 is formed on the surface of a carbon nanotube 29 or carbon nanohorn 31. , 15B can be made, the electric resistance of the electrodes 15A, 15B can be reduced, the current flows smoothly to the electrodes 15A, 15B, and sufficient electricity can be generated in the polymer electrolyte fuel cell 10. Possible solid polymer fuel It can be made capable of electrodes 15A to supply sufficient electric energy to the load connected to the pond 10 and 15B to inexpensive

Reference Signs List 10 polymer electrolyte fuel cell 11 cell 12 cell stack 13A fuel electrode (electrode)
13B Fuel electrode (electrode)
14A air electrode (electrode)
14A air electrode (electrode)
15A Carbon nanotube electrode or carbon nanohorn electrode 15B Carbon nanotube electrode or carbon nanohorn electrode 16 Solid polymer electrolyte membrane (electrode assembly membrane)
17 Separator 18 Separator 19 Membrane / electrode assembly 20 Gas diffusion layer 21 Gas diffusion layer 22 Gas seal 23 Gas seal 24 Front surface 25 Back surface 26 Alloy fine powder 27 Metal electrode thin plate 28 Carbon electrode thin plate 29 Carbon nanotube 30 Aggregate (aggregate plate)
31 Carbon nanohorn 32 Aggregate (aggregate plate)
33 Alloy fine particle laminated porous structure 34 Channel 35 Inlet 36 Conductor 37 Load 38 Transition metal 39 Transition metal fine powder (fine powder)
Reference Signs List 40 Transition metal fine powder mixture 41 Transition metal fine powder compact 42 Alloy molded product 43 Alloy fine powder L1 Thickness dimension S1 Transition metal selecting process S2 Transition metal fine powder mixture producing process S3 Transition metal fine powder compact producing process S4 Alloy molded product Production process S5 Alloy fine particle carrying process S6 Alloy fine powder production process

Claims (16)

The fuel cell further includes a cell stack having a plurality of cells, wherein the cells include a fuel electrode and an air electrode, an electrode assembly film located between the fuel electrode and the air electrode, and a fuel electrode and an air electrode. In a polymer electrolyte fuel cell formed from an outer and a separator located on the outside,
The fuel electrode and the air electrode are a carbon nanotube electrode or a carbon nanohorn electrode, and the carbon nanotube electrode or the carbon nanohorn electrode is a transition metal fine powder of at least three types of transition metals selected from various transition metals. An alloy molded article obtained by compressing a homogeneously mixed / dispersed transition metal fine powder mixture and then baked is included, and includes an aggregate of carbon nanotubes or an aggregate of carbon nanohorns. At least three types of transition metals are selected from the various transition metals so that the calculated work function of the work functions of the at least three types of transition metals approximates the work function of the platinum group element; Alternatively, in the carbon nanohorn electrode, the alloy fine particles are Polymer electrolyte fuel cell characterized by being carried on the surface or surfaces of the carbon nanohorn nanotubes.   On the surface of the carbon nanotube or the surface of the carbon nanohorn, an alloy particle laminated porous structure is formed by the alloy particles overlapping outward from the surface of the carbon nanotube or the carbon nanohorn, and in the polymer electrolyte fuel cell, 2. The polymer electrolyte fuel cell according to claim 1, wherein the electrode assembly film and the alloy fine particle laminated porous structure overlap without any gap.   The particle diameter of the transition metal fine powder is in a range of 10 μm to 200 μm, and the thickness dimension of the carbon nanotube electrode or the carbon nanohorn electrode is in a range of 0.03 mm to 0.3 mm. 9. The polymer electrolyte fuel cell according to item 1.   The transition metal fine powder mixture is mainly composed of Ni (nickel) fine powder, and the transition metal fine powder mixture has a work function of Ni and a work function of at least two other transition metals other than Ni. A transition metal fine powder of at least two other transition metals other than the Ni fine powder is selected from the various transition metals so that the composite work function of the transition metal approximates the work function of the platinum group element. The polymer electrolyte fuel cell according to any one of claims 1 to 3.   A transition metal fine powder of one type of transition metal excluding the Ni fine powder, wherein a weight ratio of the Ni (nickel) fine powder to the total weight of the transition metal fine powder mixture is in a range of 30% to 50%; Wherein the weight ratio of the transition metal fine powder mixture to the total weight of the transition metal fine powder mixture is in the range of 20% to 50%, and the transition metal fine powder of the transition metal fine powder of at least one other transition metal excluding the Ni fine powder. The polymer electrolyte fuel cell according to claim 4, wherein a weight ratio of the body mixture to the total weight is in a range of 3% to 20%.   The transition metal fine powder mixture has a fine powder of Fe (iron) as a main component, and the transition metal fine powder mixture has a work function of Fe and a work function of at least two types of transition metals other than Fe. A transition metal fine powder of at least two other transition metals other than the fine powder of Fe is selected from the various transition metals so that the composite work function of the transition metal approximates the work function of the platinum group element. The polymer electrolyte fuel cell according to any one of claims 1 to 3.   The weight ratio of the Fe (iron) fine powder to the total weight of the transition metal fine powder mixture is in the range of 30% to 50%, and the transition metal fine powder of one type of transition metal excluding the Fe fine powder Wherein the weight ratio of the transition metal fine powder mixture to the total weight of the transition metal fine powder mixture is in the range of 20% to 50%, and the transition metal fine powder of the transition metal fine powder of at least one other transition metal excluding the Fe fine powder The polymer electrolyte fuel cell according to claim 6, wherein the weight ratio of the body mixture to the total weight is in the range of 3% to 20%.   The transition metal fine powder mixture is mainly composed of Cu (copper) fine powder, and the transition metal fine powder mixture has a work function of Cu and a work function of at least two types of transition metals other than Cu. A transition metal fine powder of at least two other transition metals other than the fine powder of Cu is selected from the various transition metals so that the composite work function of the transition metal approximates the work function of the platinum group element. The polymer electrolyte fuel cell according to any one of claims 1 to 3.   The weight ratio of the Cu (copper) fine powder to the total weight of the transition metal fine powder mixture is in the range of 30% to 50%, and the transition metal fine powder of one type of transition metal excluding the Cu fine powder Wherein the weight ratio of the transition metal fine powder mixture to the total weight of the transition metal fine powder mixture is in the range of 20% to 50%, and the transition metal fine powder of at least one other transition metal except for the Cu fine powder. The polymer electrolyte fuel cell according to claim 8, wherein a weight ratio of the body mixture to the total weight is in a range of 3% to 20%.   In the alloy molded product, the transition metal fine powder of at least two types of transition metals among the selected transition metals is melted during firing of the transition metal fine powder mixture, and the transition metal fine powder of the molten transition metal is used as a binder. 10. The polymer electrolyte fuel cell according to claim 1, wherein transition metal fine powders of the transition metals are joined. In an electrode manufacturing method for manufacturing a carbon nanotube electrode or a carbon nanohorn used as a fuel electrode and an air electrode of a polymer electrolyte fuel cell,
The electrode manufacturing method may include at least three types of transition metals such that a composite work function of work functions of at least three types of transition metals selected from various types of transition metals approximates a work function of a platinum group element. Transition metal selecting step of selecting a transition metal of the above, and transition metal fine powder for uniformly mixing and dispersing transition metal fine powders of at least three types of transition metals selected in the transition metal selecting step. A mixture preparation step, a transition metal fine powder compact to produce a transition metal fine powder compact by pressing the transition metal fine powder mixture produced by the transition metal fine powder mixture preparation step at a predetermined pressure, and the transition metal An alloy molded product producing step of firing the transition metal fine powder compact produced by the fine powder compact produced process at a predetermined temperature to form an alloy molded product; An alloy fine particle carrier for generating a tube or a carbon nanohorn, evaporating the alloy molded product formed in the alloy molded product forming step, and carrying the alloy fine particles of the alloy molded product on the surface of the carbon nanotube or the surface of the carbon nanohorn. And a process for producing an electrode of a polymer electrolyte fuel cell.   The alloy fine particle supporting step evaporates an alloy molded product simultaneously with the generation of the carbon nanotube or the carbon nanohorn, and causes the alloy fine particles of the alloy molded product to be supported on the surface of the carbon nanotube or the surface of the carbon nanohorn. 3. The method for producing an electrode of a polymer electrolyte fuel cell according to item 1.   The solid polymer form according to claim 11 or 12, wherein the transition metal fine powder mixture preparation step pulverizes at least three types of transition metals selected in the transition metal selection step to a particle size of 10 µm to 200 µm. An electrode manufacturing method for a fuel cell.   12. The transition metal fine powder compressed product producing step, wherein the transition metal fine powder mixture produced in the transition metal fine powder mixture producing process is pressurized at a pressure of 500 to 800 MPa to produce the transition metal fine powder compressed product. 14. The method for producing an electrode of a polymer electrolyte fuel cell according to claim 13.   The alloy molded product forming step, the transition metal fine powder compact is fired at a temperature at which the transition metal fine powder of at least two types of transition metals selected from the transition metals selected in the transition metal selecting step is melted and melted. The method for producing an electrode of a polymer electrolyte fuel cell according to any one of claims 11 to 14, wherein the transition metal fine powder of the transition metal is joined using the transition metal fine powder of the transition metal as a binder. The alloy fine particle supporting step forms the carbon nanotube electrode or the carbon nanohorn electrode into a thickness dimension in a range of 0.03 mm to 0.3 mm, and overlaps outward from the surface of the carbon nanotube or the surface of the carbon nanohorn. The method for manufacturing an electrode of a polymer electrolyte fuel cell according to any one of claims 11 to 15, wherein the alloy fine particles form an alloy fine particle laminated porous structure.

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