JP2019220340A - electrode - Google Patents

Abstract

To provide an electrode which can be manufactured at low cost without utilizing platinum group elements and is capable of being used as an anode or a cathode with catalytic activity (catalysis).SOLUTION: An electrode 10 is an alloy thin plate electrode with a porous structure, which is formed from at least three types of transition metals selected from various types of transition metals and calcinated after compressing a metal powder mixture into a state of thin plate with a thickness dimension of 0.03 mm to 0.3 mm formed by uniformly mixing and dispersing the powder of at least the selected three types of transition metals to form a large number of fine passages. In the electrode 10, at least three types of transition metals are selected from among the various types of transition metals so that a composite work function of work functions of at least the selected three types of transition metals approximates the work function of platinum group elements.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrode used as an anode or a cathode.

  There is disclosed a fuel cell electrode including a platinum catalyst in which platinum is supported on nitrogen-doped carbon obtained by calcining a porous metal complex (PCP / MOF) containing zinc as a low boiling point metal (see Patent Document 1). Since this fuel cell electrode uses a porous metal complex (PCP / MOF) containing zinc, which is a low boiling point metal, as a raw material for production, the catalyst carrier is an NDC having a large specific surface area with almost no metal derived from the raw material. And a highly active platinum catalyst can be obtained by supporting a small amount of platinum. Further, since no metal derived from a porous metal complex (PCP / MOF), which is a production raw material, is contained, firing conditions can be freely set. That is, it is possible to control the nitrogen content and crystallinity in the obtained NDC by changing the organic compound linker of the porous metal complex (PCP / MOF) used as a raw material and adjusting the firing temperature.

JP 2018-23929 A

  Various platinum-supporting 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 suppress the amount of the platinum group element used. Further, development of inexpensive electrodes having a non-platinum catalyst using a metal 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 an electrode which can be manufactured at low cost without using a platinum group element, has catalytic activity (catalytic action), and can be used as an anode or a cathode. Another object of the present invention is to enable a fuel cell to generate sufficient electricity, supply sufficient electric energy to a load connected to the fuel cell, and efficiently perform electrolysis in a hydrogen gas generator. An object of the present invention is to provide an electrode which can be performed well and can generate a sufficient amount of hydrogen gas.

  The premise of the present invention for solving the above problems is an electrode used as an anode or a cathode.

  The feature of the present invention on the above premise is that the electrode is formed of at least three types of transition metals selected from various transition metals, and powders of at least three types of the selected transition metals are uniformly mixed and dispersed. A porous alloy thin plate electrode in which a metal powder mixture is compressed into a thin plate having a predetermined area and then fired to form a large number of fine channels, and the thickness of the porous thin alloy electrode is 0.03 mm to 0 mm. In the case of an alloy thin-plate electrode having a porous structure in the range of 0.3 mm, the work function of at least three kinds of selected transition metals is selected from various transition metals so that the work function thereof approximates the work function of the platinum group element. From at least three types of transition metals.

  As an example of the present invention, an alloy thin plate electrode having a porous structure is formed by using a Ni powder as a main component and having a thickness in a range of 0.03 mm to 0.3 mm. In order to make the work function of the function and the work function of at least two types of transition metals other than Ni close to the work function of the platinum group element, at least other types of transition metal excluding Ni powder from various transition metals are used. Two transition metal powders were selected.

  As another example of the present invention, the weight ratio of the Ni powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the metal of one type of transition metal powder excluding the Ni powder is used. The weight ratio of the powder mixture to the total weight of the powder mixture is in the range of 20% to 50%, and the weight ratio of at least one transition metal powder other than the Ni powder to the total weight of the metal powder mixture is , In the range of 3% to 20%.

  As another example of the present invention, an alloy thin plate electrode having a porous structure is formed by using a powder of Fe as a main component and having a thickness in the range of 0.03 mm to 0.3 mm. In addition to removing Fe powder from various transition metals, the composite work function of the work function of the transition metal and the work function of at least two other transition metals other than Fe approximates the work function of the platinum group element. Of at least two types of transition metals are selected.

  As another example of the present invention, the weight ratio of the Fe powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the metal of one type of transition metal powder excluding the Fe powder is used. The weight ratio with respect to the total weight of the powder mixture is in the range of 20% to 50%, and the weight ratio of the powder of at least one other transition metal excluding the powder of Fe to the total weight of the metal powder mixture is , In the range of 3% to 20%.

  As another example of the present invention, an alloy thin plate electrode having a porous structure is formed by using a Cu powder as a main component and having a thickness in a range of 0.03 mm to 0.3 mm. In addition to removing Cu powder from various transition metals, the composite work function of the work function of the transition metal and the work function of at least two other transition metals other than Cu approximates the work function of the platinum group element. Of at least two types of transition metals are selected.

  As another example of the present invention, the weight ratio of the Cu powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the metal of one type of transition metal powder excluding the Cu powder is used. The weight ratio with respect to the total weight of the powder mixture is in the range of 20% to 50%, and the weight ratio of at least one transition metal powder other than the Cu powder to the total weight of the metal powder mixture is , In the range of 3% to 20%.

  As another example of the present invention, the porosity of the porous alloy thin plate electrode is in the range of 15% to 30%.

As another example of the present invention, the density of the alloy thin electrodes of porous structure ^is in the range of ^{5.0g / cm 2 ~7.0g / cm 2} .

  As another example of the present invention, the particle size of the transition metal powder is in the range of 10 μm to 200 μm.

  As another example of the present invention, in the case of an alloy thin plate electrode having a porous structure, the powder of the transition metal having the lowest melting point is melted during firing of a metal powder mixture compressed into a thin plate having a predetermined area, and the melted transition metal is bound with a binder. As another transition metal powder.

  As another example of the present invention, the weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture is in the range of 3% to 20%.

  As another example of the present invention, the electrode is formed of various transition metals such that the composite work function of the work functions of at least three transition metals selected from various transition metals is close to the work function of the platinum group element. A transition metal selection step of selecting at least three types of transition metals from among them, and a metal powder for producing a metal powder mixture in which at least three types of transition metal powders selected by the transition metal selection step are uniformly mixed and dispersed. A mixture preparation step, a metal sheet preparation step of pressing the metal powder mixture produced by the metal powder mixture preparation step at a predetermined pressure to produce a metal sheet, and a metal sheet produced by the metal sheet preparation step at a predetermined temperature. It is manufactured by a porous alloy thin plate electrode forming step of firing to form a porous alloy thin plate electrode in which a large number of fine channels are formed.

  As another example of the present invention, in the metal powder mixture preparation step, at least three types of transition metals selected in the transition metal selection step are finely pulverized to a particle size of 10 μm to 200 μm.

  As another example of the present invention, the metal sheet preparing step includes pressing the metal powder mixture produced by the metal powder mixture producing step at a pressure of 500 MPa to 800 MPa to reduce the thickness dimension of 0.03 mm to 0.3 mm. A thin metal plate having a large number of fine channels is prepared.

  As another example of the present invention, the step of forming a porous alloy thin plate electrode includes a step of melting a metal of a transition metal powder having a lowest melting point among at least three types of transition metals selected in the transition metal selection step. The thin plate is fired.

  ADVANTAGE OF THE INVENTION According to the electrode which concerns on this invention, it is formed from at least 3 types of transition metals selected from various transition metals, and the metal which mixed and dispersed the powder of at least 3 types of these selected transition metals uniformly. An alloy thin plate electrode having a porous structure in which a powder mixture is compressed into a thin plate having a predetermined area and then fired to form a large number of fine channels (passage holes). The work function of at least three selected transition metals is selected. Since at least three transition metals are selected from various transition metals so that the composite work function of the platinum group element is close to the work function of the platinum group element, the transition metal has a work function that is substantially the same as that of the platinum group element. It can exhibit substantially the same catalytic activity (catalysis) as the group element, and can be suitably used as an anode or a cathode of a fuel cell, a hydrogen gas generator, or the like. The electrode is formed from at least three transition metals selected from various transition metals, does not utilize expensive platinum group elements, and can make non-platinum anodes or cathodes inexpensive. Since the electrode has a porous alloy thin plate electrode having a thickness in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode is low, protons can move smoothly through the electrode, and the electrode can be used in a fuel cell. By using, sufficient electricity can be generated in the fuel cell, sufficient electrical energy can be supplied to the load connected to the fuel cell, and by using the electrode in the hydrogen gas generator, Electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated.

  An alloy thin plate electrode having a porous structure is formed by using Ni powder as a main component and having a thickness in the range of 0.03 mm to 0.3 mm, and has a work function of Ni and a work function of at least two types of transition metals other than Ni. The electrode in which at least two types of transition metal powders other than Ni powder are selected from various transition metals so that the composite work function thereof is close to the work function of the platinum group element, Excluding Ni powder from various transition metals so that the composite work function of the work function of Ni and the work function of at least two other transition metals other than Ni approximates the work function of a platinum group element. Since at least two types of transition metal powders are selected, they have substantially the same work function as the platinum group element, and can exhibit almost the same catalytic activity (catalysis) as the platinum group element, Fuel cell and hydrogen gas generator It can be suitably used as an anode or cathode and the like. The electrode is formed of Ni powder and at least two types of transition metal powder other than Ni powder selected from various transition metals, and expensive platinum group elements are used. In addition, a non-platinum anode or cathode can be manufactured at low cost. Since the thickness of the electrode of the alloy thin plate having a porous structure containing Ni as a main component is in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode is low, and protons can move smoothly through the electrode. By using the electrode in the fuel cell, sufficient electricity can be generated in the fuel cell, sufficient electric energy can be supplied to the load connected to the fuel cell, and the electrode can be used as a hydrogen gas generator. In this case, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated.

  The weight ratio of the Ni powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the weight ratio of one transition metal powder excluding the Ni powder to the total weight of the metal powder mixture is The electrode in the range of 20% to 50% and the weight ratio of the powder of at least one other transition metal excluding the Ni powder to the total weight of the metal powder mixture in the range of 3% to 20% is , Ni powder is selected from various transition metals so that a composite work function of a work function of Ni and a work function of at least two types of transition metals other than Ni approximates a work function of a platinum group element. At least two other transition metal powders are selected, and the weight ratio of the Ni powder, the weight ratio of at least one transition metal powder excluding the Ni powder, and the Ni powder The weight ratio of at least one other transition metal powder excluding By setting it within the range, it has a work function substantially the same as that of the platinum group element, and can exhibit substantially the same catalytic activity (catalysis) as the platinum group element. It can be suitably used. The electrode is formed from the powder of Ni in the above weight ratio and the powder of at least two kinds of transition metals in the above weight ratio excluding Ni selected from various transition metals, and an expensive platinum group element is used. In addition, a non-platinum anode or cathode can be produced at low cost.

  An alloy thin plate electrode having a porous structure is formed to have a thickness of 0.03 mm to 0.3 mm with Fe powder as a main component, and has a work function of Fe and a work function of at least two types of transition metals other than Fe. An electrode in which at least two types of transition metal powders other than Fe powders are selected from various transition metals so that the composite work function thereof is close to the work function of the platinum group element, Excluding Fe powder from various transition metals so that the composite work function of the work function of Fe and the work function of at least two other transition metals other than Fe approximates the work function of a platinum group element. Since at least two types of transition metal powders are selected, they have substantially the same work function as the platinum group element, and can exhibit almost the same catalytic activity (catalysis) as the platinum group element, Fuel cell and hydrogen gas generator It can be suitably used as an anode or cathode and the like. The electrode is made of Fe powder and at least two kinds of transition metal powders other than Fe powder selected from various transition metals, and expensive platinum group elements are used. In addition, a non-platinum anode or cathode can be manufactured at low cost. The electrode has a porous alloy thin plate electrode containing Fe as a main component, and the thickness of the electrode is in the range of 0.03 mm to 0.3 mm. Therefore, the electric resistance of the electrode is low, and protons can move smoothly through the electrode. By using the electrode in the fuel cell, sufficient electricity can be generated in the fuel cell, sufficient electric energy can be supplied to the load connected to the fuel cell, and the electrode can be used as a hydrogen gas generator. In this case, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated.

  The weight ratio of the Fe powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the weight ratio of one transition metal powder excluding the Fe powder to the total weight of the metal powder mixture. Wherein the weight ratio of at least one transition metal powder other than Fe powder to the total weight of the metal powder mixture is in the range of 3% to 20%. Is a powder of Fe from various transition metals so that 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 approximates the work function of a platinum group element. And at least two types of transition metal powders except for the Fe powder, the weight ratio of the Fe powder, the weight ratio of at least one transition metal powder excluding the Fe powder, and the Fe powder Weight ratio of powder of at least one other transition metal excluding body When the content is within the above range, the catalyst has substantially the same work function as the platinum group element, and can exhibit substantially the same catalytic activity (catalysis) as the platinum group element. It can be suitably used as a cathode. The electrode is formed from the powder of Fe in the weight ratio and the powder of at least two types of transition metals in the weight ratio excluding Fe selected from various transition metals, and an expensive platinum group element is used. In addition, a non-platinum anode or cathode can be produced at low cost.

  An alloy thin plate electrode having a porous structure is formed by using a Cu powder as a main component to a thickness of 0.03 mm to 0.3 mm, and has a work function of Cu and a work function of at least two types of transition metals other than Cu. An electrode in which at least two types of transition metal powders other than the Cu powder are selected from various transition metals so that the composite work function thereof is close to the work function of the platinum group element, Excluding Cu powder from various transition metals so that the composite work function of the work function of Cu and the work function of at least two other transition metals other than Cu approximates the work function of a platinum group element. Since at least two types of transition metal powders are selected, they have substantially the same work function as the platinum group element, and can exhibit almost the same catalytic activity (catalysis) as the platinum group element, Fuel cell and hydrogen gas generator It can be suitably used as an anode or cathode and the like. The electrode is formed of a powder of Cu and at least two types of transition metal powder other than a powder of Cu selected from various transition metals, and uses an expensive platinum group element. In addition, a non-platinum anode or cathode can be manufactured at low cost. Since the thickness of the electrode of the alloy thin plate electrode having a porous structure containing Cu as a main component is in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode is low, and protons can move smoothly through the electrode. By using the electrode in the fuel cell, sufficient electricity can be generated in the fuel cell, sufficient electric energy can be supplied to the load connected to the fuel cell, and the electrode can be used as a hydrogen gas generator. In this case, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated.

  The weight ratio of the Cu powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the weight ratio of one transition metal powder excluding the Cu powder to the total weight of the metal powder mixture is The electrode in the range of 20% to 50% and the weight ratio of the powder of at least one other transition metal excluding the powder of Cu to the total weight of the metal powder mixture in the range of 3% to 20% A Cu powder is selected from various transition metals so that a composite work function of a work function of Cu and a work function of at least two types of transition metals other than Cu approximates a work function of a platinum group element. At least two other transition metal powders are selected, and the weight ratio of the Cu powder, the weight ratio of at least one transition metal powder excluding the Cu powder, and the Cu powder The weight ratio of at least one other transition metal powder excluding Within this range, the catalyst has a work function substantially the same as that of the platinum group element, and can exhibit substantially the same catalytic activity (catalysis) as that of the platinum group element. The anode or cathode of a fuel cell, a hydrogen gas generator, etc. Can be suitably used. The electrode is formed from the above-mentioned weight ratio of Cu powder and at least two kinds of transition metal powder of the above-mentioned weight ratio excluding Cu selected from various transition metals, and an expensive platinum group element is used. In addition, a non-platinum anode or cathode can be produced at low cost.

  When the porosity of the porous alloy thin plate electrode is in the range of 15% to 30%, by setting the porosity of the alloy thin plate electrode in the above range, the porous thin alloy plate electrode can have a large number of fine channels ( (Porous holes), which can increase the specific surface area of the alloy thin plate electrode, and allow the gas or liquid to flow through these flow paths to make the gas or liquid contact the contact surface of the alloy thin plate electrode widely. And the catalyst activity (catalytic action) substantially similar to that of the platinum group element can be surely exhibited. The electrode can use its catalytic function sufficiently and reliably and can be suitably used as a non-platinum anode or cathode having catalytic activity (catalytic activity).

Electrode density of alloy thin electrodes of porous structure is in the range of 5.0g ^/ cm ² ~7.0g / cm 2, by making the density of the alloy sheet electrode on the range, alloy thin electrodes of porous structure are many Is formed into a porous material having fine flow passages (passage holes), and the specific surface area of the alloy thin plate electrode can be increased. The gas or liquid flows through those flow passages while the gas or liquid contacts the alloy thin plate electrode. Thus, the catalyst can be brought into wide contact with the surface, and the catalyst activity (catalysis) substantially similar to that of the platinum group element can be surely exhibited. The electrode can utilize its catalytic function sufficiently and reliably and can be suitably used as a non-platinum anode or cathode having catalytic activity (catalytic activity).

  In an electrode in which the particle diameter of the transition metal powder is in the range of 10 μm to 200 μm, by setting the particle diameter of the transition metal in the above range, the alloy thin plate electrode having the porous structure can form a large number of fine channels (passage holes). It is possible to increase the specific surface area of the alloy thin plate electrode, and it is possible to make the gas and liquid flow widely through the flow path of the alloy thin plate electrode and the contact surface of the alloy thin plate electrode, The catalyst activity (catalysis) substantially similar to that of the platinum group element can be surely exhibited. The electrode can use its catalytic function sufficiently and reliably and can be suitably used as a non-platinum anode or cathode having catalytic activity (catalytic activity).

  The electrode in which the transition metal powder having the lowest melting point is melted during firing of the metal powder mixture compressed into a thin plate having a predetermined area, and the other transition metal powder is joined using the molten transition metal as a binder, By joining the other powdery metal with the powdery metal having the lowest melting point as a binder, the electrode has a high strength and can maintain its shape, and the electrode when the electrode is impacted Can be prevented from being damaged or damaged. Since the electrode can maintain its shape, it is possible to use its catalytic function sufficiently and reliably, and it is preferable to use it suitably as a non-platinum anode or cathode having catalytic activity (catalytic activity). it can.

  The electrode in which the weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture is in the range of 3% to 20% is such that the weight ratio of the transition metal powder serving as the binder is in the above range. Even if the transition metal serving as the binder is melted, the fine flow path (passage hole) of the porous alloy thin plate electrode is not blocked, and the porous structure of the alloy thin plate electrode can be maintained. The catalyst function can be used sufficiently and reliably, and it can be suitably used as a non-platinum anode or cathode having catalytic activity (catalysis).

  A transition that selects at least three types of transition metals from various types of transition metals so that a work function of at least three types of transition metals selected from various types of transition metals is close to the work function of a platinum group element. A metal selection step, a metal powder mixture creation step of uniformly mixing and dispersing at least three types of transition metal powders selected in the transition metal selection step, and a metal powder mixture creation step. A step of forming a metal sheet by pressing the prepared metal powder mixture at a predetermined pressure to form a metal sheet, and firing the metal sheet formed by the metal sheet preparation step at a predetermined temperature to form a large number of fine channels (passage holes). The electrode manufactured by the porous alloy thin plate electrode forming process of forming a porous alloy thin plate electrode having the above-mentioned) is formed by a transition metal selecting process or a metal powder mixture forming process. In this way, a non-platinum electrode that does not use a platinum group element can be produced at a low cost by the metal thin plate manufacturing process and the porous structure thin metal plate electrode manufacturing process, and the catalytic function can be sufficiently and reliably used, and the catalytic activity can be improved. A non-platinum electrode that has (catalytic action) and can be used as an anode or a cathode can be produced.

  The electrode for pulverizing at least three types of transition metals selected by the transition metal selection step in the metal powder mixture preparation step into particles having a particle size of 10 μm to 200 μm, by pulverizing the transition metal to a particle diameter in the above range, A porous alloy thin plate electrode having a large specific surface area can be manufactured by molding into a porous material having a large number of fine channels (passage holes), and the gas or liquid flows through these channels to form an alloy. This makes it possible to widely contact the contact surface of the thin plate electrode, and it is possible to produce an electrode capable of reliably exhibiting substantially the same catalytic activity (catalytic action) as a platinum group element. The electrode is capable of fully and reliably utilizing its catalytic function, has a catalytic activity (catalytic action), and forms a non-platinum porous alloy thin plate electrode which can be used as an anode or a cathode. be able to.

  The thin metal plate making step presses the metal powder mixture produced by the metal powder mixture producing step at a pressure of 500 Mpa to 800 Mpa to form a large number of fine channels having a thickness of 0.03 mm to 0.3 mm. The electrode for forming the formed metal thin plate is formed by pressing (compressing) the metal powder mixture at a pressure in the above-mentioned range, and having a thickness of 0.03 mm to 0.3 mm and a large number of fine channels (passage holes). ), And an alloy thin plate electrode having a non-platinum porous structure without using a platinum group element can be manufactured at a low cost. The electrode is capable of fully and reliably utilizing its catalytic function, has a catalytic activity (catalytic action), and forms a non-platinum porous alloy thin plate electrode which can be used as an anode or a cathode. be able to. The electrode has a thickness in the range of 0.03 mm to 0.3 mm, and by forming a large number of fine channels (passage holes), the electric resistance of the electrode can be reduced, and the electrode can be formed by protons. Can move smoothly, and by using the electrodes in the fuel cell, it is possible to generate sufficient electricity in the fuel cell and supply sufficient electric energy to the load connected to the fuel cell Electrode can be made. By using the electrode in a hydrogen gas generator, the electrode can be efficiently electrolyzed, and an electrode capable of generating a sufficient amount of hydrogen gas can be produced.

  The electrode for firing the metal sheet at a temperature at which the powder of the transition metal having the lowest melting point of the at least three types of transition metals selected in the transition metal selection step is used in the porous structure alloy sheet electrode forming step is the most melting point. By joining other transition metal powders using low transition metal powder as a binder, the electrode has high strength and can maintain its shape, preventing inadvertent breakage and damage Electrode can be made. Since the electrode can maintain its shape, it is possible to use its catalytic function sufficiently and reliably, and it is preferable to use it suitably as a non-platinum anode or cathode having catalytic activity (catalytic activity). Possible electrodes can be made.

FIG. 2 is a perspective view of an electrode shown as an example. FIG. 3 is a partially enlarged front view showing an example of an electrode. FIG. 9 is a partially enlarged front view showing another example of the electrode. FIG. 3 is an exploded perspective view showing an example of a cell using electrodes. FIG. 4 is a side view of a cell using electrodes. The figure explaining the electric power generation of the fuel cell (polymer electrolyte fuel cell) using the electrode. The figure which shows the result of the electromotive force test of an electrode. The figure which shows the result of the IV characteristic test of an electrode. The figure explaining the electrolysis of the hydrogen gas generator using an electrode. FIG. 4 is a diagram illustrating a method for manufacturing the electrode 10.

  The details of the electrode according to the present invention will be described below with reference to the accompanying drawings such as FIG. 1 which is a perspective view of the electrode 10 shown as an example. FIG. 2 is a partially enlarged front view showing an example of the electrode 10, and FIG. 3 is a partially enlarged front view shown as another example of the electrode 10. In FIG. 1, the thickness direction is indicated by an arrow X, and the radial direction is indicated by an arrow Y.

  The electrode 10 is used as an anode (anode) or a cathode (cathode), and is used as an electrode (catalyst) of the fuel cell 20 (see FIG. 6) and an electrode (catalyst) of the hydrogen gas generator 29 (see FIG. 9). . The electrode 10 has a front surface 12 and a rear surface 13, has a predetermined area and a predetermined thickness L1, and is formed into a circular planar shape. The electrode 10 is an alloy thin plate electrode 15 having a porous structure having a large number of fine channels 14 (passage holes). Gas or liquid flows through the flow path 14. In addition, the planar shape of the electrode 10 is not particularly limited, and may be formed into any other planar shape in addition to the circular shape.

  The electrode 10 is formed from at least three types of transition metals selected from powdered transition metals. As the transition metal, 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.

  In the electrode 10 (alloy thin-plate electrode 15 having a porous structure), the work function of at least three kinds of selected transition metals (energy required to extract electrons from a substance) is close to the work function of a platinum group element. Thus, at least three types of transition metals are selected from the transition metals. 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).

  The electrode 10 has at least three kinds of transition metal powders selected from various transition metals (Ti (titanium) processed into a powder form, Cr (chromium) processed into a powder form, powder processed into a powder form). Mn (manganese), powdered Fe (iron), powdered Co (cobalt), powdered Ni (nickel), powdered Cu (copper), Powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver)) are uniformly mixed and dispersed. The metal powder mixture 16 is compressed into a thin plate having a predetermined area to form a thin metal plate 11, and the thin metal plate 11 is fired (see FIG. 10). The electrode 10 has a large number of fine channels 14 (passage holes) having different diameters. The electrode 10 has a large specific surface area because a large number of fine channels 14 (passage holes) are formed.

  The flow passages 14 (passage holes) have a plurality of flow openings 17 opening to the front surface 12 and a plurality of flow openings 17 opening to the rear surface 13. 10 penetrates. The flow paths 14 extend between the front surface 12 and the rear surface 13 of the electrode 10 while being bent irregularly in the thickness direction of the electrode 10, and extend from the outer peripheral edge 18 of the electrode 10 toward the center. It extends while bending in the direction irregularly. The flow paths 14 that are adjacent to each other in the radial direction and extend in the thickness direction are partially connected in the radial direction, and one flow path 14 and the other flow path 14 communicate with each other. The flow paths 14 that extend adjacent to the thickness direction and bend in the radial direction are partially connected in the thickness direction, and one flow path 14 and the other flow path 14 communicate with each other.

  The opening areas (opening diameters) of the flow passages 14 (passage holes) are not uniform in the thickness direction, are irregularly changed in the thickness direction, and are not uniform in the radial direction. , Changing irregularly in the radial direction. These flow paths 14 are irregularly opened in the thickness direction and the radial direction while the opening area (opening diameter) increases or decreases. Further, the opening area (opening diameter) of the flow opening 17 opening on the front surface 12 and the opening 17 on the rear surface 13 are not uniform, and the areas are different. The opening diameters of the flow passages 14 (passage holes) and the opening diameters of the flow openings 17 in the front and rear surfaces 12 and 13 are in the range of 1 μm to 100 μm.

  The electrode 10 (porous alloy thin plate electrode 15) has a thickness L1 in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm. If the thickness L1 of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is less than 0.03 mm, the strength is reduced, and the electrode 10 is easily broken or damaged when an impact is applied, and maintains its shape. You may not be able to. If the thickness L1 of the electrode 10 (the alloy thin plate electrode 15 having a porous structure) exceeds 0.3 mm, the electric resistance of the electrode 10 becomes large, protons cannot move smoothly through the electrode 10, and the electrode 10 When used for the battery 20, the fuel cell 20 cannot generate sufficient electricity, and cannot supply sufficient electric energy to the load 28 connected to the fuel cell 20. In addition, when the electrode 10 is used in the hydrogen gas generator 29, electrolysis cannot be performed efficiently, and the hydrogen gas generator 29 cannot generate sufficient hydrogen gas.

  Since the thickness of the electrode 10 (alloy thin plate electrode having a porous structure) is in the range of 0.03 mm to 0.3 mm, the electrode 10 has high strength and can maintain its shape. It is possible to prevent the electrode 10 from being damaged or damaged when an impact is applied. Further, the electric resistance of the electrode 10 is low, protons can move smoothly in the electrode 10, and by using the electrode 10 for the fuel cell 20, sufficient electricity can be generated in the fuel cell 20, Sufficient electric energy can be supplied to the load 28 connected to the battery 20. In addition, by using the electrode 10 in the hydrogen gas generator 29, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated in the hydrogen gas generator 29.

  The electrode 10 (the alloy thin plate electrode 15 having a porous structure) has a porosity in a range of 15% to 30%, preferably 20% to 25%, and a relative density in a range of 70% to 85%. Preferably, it is in the range of 75% to 80%. If the porosity of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is less than 15% and the relative density exceeds 85%, a large number of fine flow paths 14 (passage holes) are not formed in the electrode 10, and the electrode 10 The specific surface area of No. 10 cannot be increased. When the porosity of the electrode 10 (alloy thin plate electrode 15 having a porous structure) exceeds 30% and the relative density is less than 70%, the opening area (opening diameter) of the flow passage 14 (passage hole) and the front and rear surfaces 12 and 13 are reduced. The opening area (opening diameter) of the flow opening 17 becomes unnecessarily large, the strength of the electrode 10 is reduced, and the electrode 10 is easily damaged or damaged when an impact is applied, and the shape of the electrode 10 is maintained. It may not be possible.

  Since the porosity and the relative density of the electrode 10 (alloy thin plate electrode 15 having a porous structure) are in the above-described ranges, the electrode 10 has a large number of fine flow paths 14 (passage holes) and openings having different opening areas (opening diameters). The electrode 10 is formed into a porous shape having a number of fine front and rear surfaces 12 and 13 having different areas (opening diameters), and the specific surface area of the electrode 10 can be increased. While the gas or the liquid flows, the gas or the liquid can be brought into wide contact with the contact surface of the electrode 10 (alloy thin plate electrode 15 having a porous structure).

Electrode 10 (alloy thin plate electrode 15 of the porous structure) in the range that the density of ^{5.0g / cm 2 ~7.0g / cm 2} , preferably in ^the range of 5.5g / cm ² ~6.5g / cm 2 It is in. When the density of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is less than 5.0 g / cm ² , the strength of the electrode 10 is reduced, and the electrode 10 is easily damaged or damaged when an impact is applied, and its shape is reduced. May not be able to maintain. When the density of the electrode 10 (alloy thin plate electrode 15 having a porous structure) exceeds 7.0 g / cm ² , a large number of fine channels 14 (passage holes) are not formed in the electrode 10, and the specific surface area of the electrode 10 increases. Can not do it.

  Since the density of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is within the above range, the electrode 10 has a large number of fine flow paths 14 (passage holes) and opening areas (opening diameters) having different opening areas (opening diameters). ) Having a large number of fine front and rear surfaces 12, 13, which are formed into a porous material having a large number of flow ports 17. The specific surface area of the electrode 10 can be increased, and gas and liquid can flow through these flow paths 14 (passage holes). The gas or the liquid can be brought into wide contact with the contact surface of the electrode 10 (the alloy thin plate electrode 15 having a porous structure) while flowing.

  Ti powder (powder processed Ti), Cr powder (powder processed Cr), Mn powder (powder processed Mn), Fe powder (powder processed) Processed Fe), Co powder (Co processed into powder), Ni powder (Ni processed into powder), Cu powder (Cu processed into powder), Zn powder Powder (Zn processed into powder), Nb powder (Nb processed into powder), Mo powder (Mo processed into powder), Ag powder (processed into powder) Ag) has a particle size in the range of 10 μm to 200 μm.

  If the particle diameter of the transition metal powder is less than 10 μm, the flow path 14 (passage hole) is blocked by the transition metal, so that many fine flow paths 14 cannot be formed in the electrode 10 and the electrode 10 ( The specific surface area of the porous alloy thin plate electrode 15) cannot be increased. If the particle diameter of the transition metal powder exceeds 200 μm, the opening area (opening diameter) of the flow path 14 (passage hole) and the opening area (opening diameter) of the flow opening 17 of the front and rear surfaces 12 and 13 are more than necessary. Therefore, a large number of fine channels 14 cannot be formed in the electrode 10 (alloy thin plate electrode 15 having a porous structure), and the specific surface area of the electrode 10 cannot be increased.

  In the electrode 10 (alloy thin plate electrode 15 having a porous structure), since the particle diameter of the transition metal powder is in the above-mentioned range, the electrode 10 has a large number of fine flow paths 14 (passage holes) having different opening areas (opening diameters). ) And a large number of fine front and rear surfaces 12 and 13 having different opening areas (opening diameters), and formed into a porous material having a large number of flow ports 17, so that the specific surface area of the electrode 10 can be increased. The gas or the liquid can be brought into wide contact with the contact surface of the electrode 10 (the alloy thin plate electrode 15 having a porous structure) while the gas or the liquid flows.

  FIG. 4 is an exploded perspective view showing an example of the cell 19 using the electrode 10, and FIG. 5 is a side view of the cell 19 using the electrode 10. FIG. 6 is a diagram for explaining power generation of the fuel cell 20 (polymer electrolyte fuel cell) using the electrode 10, and FIG. 7 is a diagram showing a result of an electromotive force test of the electrode 10. FIG. 8 is a diagram showing a result of an IV characteristic test of the electrode 10.

  As an example of the cell 19 using the electrode 10, as shown in FIG. 4, a fuel electrode 21 (anode) using the electrode 10, an air electrode 22 (cathode) using the electrode 10, a fuel electrode 21 and air The solid polymer electrolyte membrane 23 (fluorine-based ion exchange membrane) interposed between the electrodes 22, the separator 24 a (bipolar plate) located outside the fuel electrode 21 in the thickness direction, and the separator 24 a located outside the thickness direction of the air electrode 22. And a separator 24b (bipolar plate). A supply channel for a reaction gas (hydrogen, oxygen, etc.) is carved (carved) in the separators 24a, 24b.

  In the cell 19, as shown in FIG. 5, the fuel electrode 21, the air electrode 22, and the solid polymer electrolyte membrane 23 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly (Membrane Electrode Assembly, MEA). The membrane / electrode assembly is sandwiched between the separators 24a and 24b. In the fuel cell 20 (polymer electrolyte fuel cell), a plurality of cells 19 (single cells) overlap in one direction and are connected in series to form a cell stack (fuel cell stack). The solid polymer electrolyte membrane 23 has proton conductivity and no electronic conductivity.

  A gas diffusion layer 25a is formed between the fuel electrode 21 and the separator 24a, and a gas diffusion layer 25b is formed between the air electrode 22 and the separator 24b. A gas seal 26a is provided between the fuel electrode 21 and the separator 24a and above and below the gas diffusion layer 25. A gas seal 26b is provided between the air electrode 22 and the separator 24b and above and below the gas diffusion layer 25b.

In the fuel cell 20 (polymer electrolyte fuel cell), as shown in FIG. 6, hydrogen (fuel) is supplied to the fuel electrode 21 (electrode 10), and air (oxygen) is supplied to the air electrode 22 (electrode 10). Is done. At the fuel electrode 21 (electrode 10), hydrogen is decomposed into protons (hydrogen ions, H ⁺ ) and electrons by a reaction (catalysis) of H ₂ → 2H ⁺ + 2e ⁻ . Thereafter, the protons move to the air electrode 22 (electrode 10) through the solid polymer electrolyte membrane 23, and the electrons move to the air electrode 22 through the conductor 27. Protons generated at the fuel electrode 21 flow through the solid polymer electrolyte membrane 23. At the air electrode 22 (electrode 10), the protons transferred from the solid polymer electrolyte membrane 23 and the electrons transferred on the conducting wire 27 react with oxygen in the air, and water is formed by the reaction of 4H ⁺ + O ₂ + 4e → 2H ₂ O. Generated. The fuel electrode 21 (electrode 10) and the air are prepared from at least three types of transition metals selected from transition metals so that the composite work function of the work functions of at least three types of transition metals approximates the work function of the platinum group element. Since the electrode 22 (electrode 10) is formed, the fuel electrode 21 and the air electrode 22 exhibit excellent catalytic activity (catalysis), and hydrogen is efficiently decomposed into protons and electrons.

  In the electromotive voltage test, a voltage (V) between the fuel electrode 21 (electrode 10) and the air electrode 22 (electrode 10) was measured for 15 minutes after hydrogen gas injection. In the diagram showing the results of the electromotive force test in FIG. 7, the horizontal axis represents the measurement time (min), and the vertical axis represents the voltage (V) between the fuel electrode 21 (electrode 10) and the air electrode 22 (electrode 10). Represents In a fuel cell using an electrode (platinum electrode) using (supporting) platinum, as shown in FIG. 7 showing the result of an electromotive force test, the voltage between the electrodes is about 1.079 (V). In contrast, in the fuel cell 20 using the electrode 10 (non-platinum electrode), the voltage (electromotive force) between the fuel electrode 21 (electrode 10) and the air electrode 22 (electrode 10) is 1.01 (electromotive force). V) to 1.02 (V).

  In the IV characteristic test, a load was connected between the fuel electrode 21 (electrode 10) and the air electrode 22 (electrode 10), and the relationship between voltage and current was measured. In FIG. 8 showing the results of the IV characteristic test, the horizontal axis represents current (A), and the vertical axis represents voltage (V). In the fuel cell using the electrode 10 (non-platinum electrode), as shown in FIG. 8 showing the result of the IV characteristic test, the voltage drop of the fuel cell using the electrode carrying platinum (platinum electrode) is shown. The result was not much different from the rate. As shown in the result of the electromotive force test in FIG. 7 and the result of the IV characteristic test in FIG. 8, the non-platinum electrode 10 that does not use a platinum group element emits electrons to generate hydrogen ions. It has been confirmed that it has a catalytic action to promote and has substantially the same oxygen reduction function (catalytic action) as an electrode using platinum.

  The electrode 10 is formed of a metal powder mixture 16 formed of at least three types of transition metals selected from various transition metals, and uniformly mixed and dispersed with at least three types of selected transition metal powders. An alloy thin plate electrode 15 having a porous structure in which a large number of fine flow paths 14 (passage holes) are formed by being compressed into a thin plate having a predetermined area and then baked to synthesize work functions of at least three selected transition metals. Since at least three types of transition metals are selected from various transition metals so that the work function approximates the work function of the platinum group element, the transition metal has substantially the same work function as the platinum group element. It can exhibit substantially the same catalytic activity (catalysis) as that of the fuel cell 20, and can be suitably used as the fuel electrode 21 (anode) and the air electrode 22 (cathode) of the fuel cell 20.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) is formed of at least three types of transition metals selected from various transition metals, does not use an expensive platinum group element, and is a non-platinum fuel electrode. 21 (anode) and air electrode 22 (cathode) can be manufactured at low cost. Since the thickness of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode 10 is low, and protons can move smoothly through the electrode 10. By using the electrode 10 for the fuel cell 20, sufficient electricity can be generated in the fuel cell 20, and sufficient electric energy can be supplied to the load 28 connected to the fuel cell 20.

  FIG. 9 is a diagram illustrating electrolysis of the hydrogen gas generator 29 using the electrode 10. As an example of the hydrogen gas generator 29 using the electrode 10, as shown in FIG. 9, an anode 30 (anode) using the electrode 10, a cathode 31 (cathode) using the electrode 10, an anode 30 and a cathode A solid polymer electrolyte membrane 32 (fluorine-based ion exchange membrane) interposed between the first and second electrodes 31, an anode power supply member 33a and a cathode power supply member 33b, an anode water storage tank 34a and a cathode water storage tank 34b, and an anode main electrode 35a And a cathode main electrode 35b.

  In the hydrogen gas generator 29, the anode 30, the cathode 31, and the solid polymer electrolyte membrane 32 overlap in the thickness direction and are integrated to constitute a membrane / electrode assembly (Membrane Electrode Assembly, MEA). The anode power supply member 33a and the cathode power supply member 33b are sandwiched. The solid polymer electrolyte membrane 32 has proton conductivity and no electronic conductivity. The anode power supply member 33a is located outside the anode 30 and is in close contact with the anode 30, and supplies a positive current to the anode 30. The anode water storage tank 34a is located outside the anode power supply member 33a and is in close contact with the anode power supply member 33a. The anode main electrode 35a is located outside the anode water storage tank 34a and supplies a positive current to the anode power supply member 33a. The cathode power supply member 33b is located outside the cathode 31 and is in close contact with the cathode 31, and supplies a negative current to the cathode 31. The cathode water storage tank 34b is located outside the cathode power supply member 33b and is in close contact with the cathode power supply member 33b. The cathode main electrode 35b is located outside the cathode water storage tank 34b and supplies a negative current to the cathode power supply member 33b.

In the hydrogen gas generator 20, as shown by arrows in FIG. 9, water (H ₂ O) is supplied to the anode water storage tank 34a and the cathode water storage tank 34b, and a positive current is supplied from the power supply to the anode main electrode 35a. At the same time, a negative current is supplied from the power supply to the cathode main electrode 35b. The positive current supplied to the anode main electrode 35a is supplied from the anode power supply member 33a to the anode 30 (anode), and the negative current supplied to the cathode main electrode 35b is supplied from the cathode power supply member 33b to the cathode 31 (cathode). Is done. At the anode 30 (electrode 10), oxygen is generated by the anodic reaction (catalysis) of 2H ₂ O → 4H ⁺ + 4e ⁻ + O ₂ , and at the cathode 31 (electrode 10), the cathode reaction of 4H ⁺ + 4e ⁻ → 2H ₂ ( Oxygen is generated by the catalytic action. Protons (hydrogen ions: H ⁺ ) move through the solid polymer electrolyte membrane 32 to the cathode 31 (electrode 10). Protons generated at the anode 30 flow through the solid polymer electrolyte membrane 32. The anode 30 (electrode 10) and the cathode 31 are prepared from at least three types of transition metals selected from transition metals so that the composite work function of the work functions of at least three types of transition metals approximates the work function of the platinum group element. Since the (electrode 10) is formed, the anode 30 and the cathode 31 exhibit excellent catalytic activity (catalytic action).

  As an example of the electrode 10 formed from a transition metal, a powdered Ni (nickel) powder is used as a main component, and the Ni powder and other transition metal processed into a powdered form other than Ni ( Powdery Ti (titanium), powdery Cr (chromium), powdery Mn (manganese), powdery Fe (iron), powdery Co (cobalt), powdery Cu (copper), powdery Metal powder obtained by uniformly mixing and dispersing powders of Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), and powdered Ag (silver). The mixture 16 is compressed into a thin plate having a predetermined area, and the metal powder mixture 16 is fired to form a porous metal sheet 15 having a large number of fine channels 14 (pass holes).

  The electrode 10 mainly composed of Ni (nickel) powder (alloy thin plate electrode 15 having a porous structure) is formed into a porous thin plate having a large number of fine channels 14 (passage holes), and has a thickness dimension. Is in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm. The electrode 10 mainly composed of Ni powder (the alloy thin plate electrode 15 having a porous structure) has a composite work function of the work function of Ni and the work function of at least two types of transition metals other than Ni, which is a platinum group element. Are selected from at least two types of transition metals other than the Ni powder from various transition metals so as to approximate the work function of the transition metal. In the electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Ni powder, the transition metal powder having the lowest melting point is melted during firing of the metal powder mixture 16 compressed into a thin plate having a predetermined area. The powder of another transition metal is joined using the molten transition metal as a binder.

  In the electrode 10 mainly composed of Ni (nickel) powder (alloy thin plate electrode 15 having a porous structure), the weight ratio of the powdered Ni metal powder mixture 16 to the total weight of the metal powder mixture 16 is 30% to 50%. , At least one kind of transition metal (powder Ti (titanium), powdery Cr (chromium), powdery Mn (manganese), powdery Fe (iron) excluding Ni Of powdery Co (cobalt), powdery Cu (copper), powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver) At least one type of metal powder mixture 16 is in the range of 20% to 50% with respect to the total weight, and at least one other type of transition metal (powder Ti (Titanium), powdered Cr (chromium), powdered Mn (manganese), powdered Fe (iron), powdered Co (cobalt), powdered Cu (copper), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag ( The weight ratio of the metal powder mixture 16 of at least one of (silver) to the total weight is in the range of 3% to 20%. The weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture 16 is in the range of 3% to 20%.

  Specific examples of the electrode 10 containing Ni (nickel) powder as a main component include metal powder obtained by uniformly mixing and dispersing Ni powder, Cu (copper) powder, and ZN (zinc) powder. The alloy thin plate electrode 15 having a porous structure in which a plurality of fine channels 14 (passage holes) are formed by compressing the mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a weight ratio of the Ni powder of 48% to the total weight of the metal powder mixture 16, a Cu powder weight ratio of 42% to the total weight of the metal powder mixture 16, The powder weight ratio of Zn to the total weight 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 Zn powder is melted, and the molten Zn serves as a binder to form Ni powder and Cu. And powder.

  Other specific examples of the electrode 10 mainly composed of Ni (nickel) powder include a metal in which Ni powder, Mn (manganese) powder, and Mo (molybdenum) powder are uniformly mixed and dispersed. An alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing a powder mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a weight ratio of the Ni powder of 48% to the total weight of the metal powder mixture 16, a powder weight ratio of Mn to the total weight of the metal powder mixture 16 of 7%, The powder weight ratio of Mo to the total weight 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 powder is melted, and the molten Mn serves as a binder to form Ni powder and Mo powder. Are joined.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) formed of a powder of Ni (nickel) as a main component and having a thickness in the range of 0.03 mm to 0.3 mm has a work function of Ni and other than Ni. At least two types of transition metal powder excluding Ni powder from various transition metals so that the composite work function of at least two types of transition metals and the work function of the transition metal approximates the work function of the platinum group element. Since the body is selected, it has substantially the same work function as the platinum group element, and can exhibit substantially the same catalytic activity (catalytic action) as the platinum group element, such as the fuel cell 20 and the hydrogen gas generator 29. Can be suitably used as the fuel electrode 20, anode 30 (anode) or air electrode 21, and cathode 31 (cathode).

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) is formed of Ni powder and at least two types of transition metal powder other than Ni powder selected from various transition metals, Since expensive platinum group elements are not used, the non-platinum fuel electrode 20, anode 30, air electrode 21, and cathode 31 can be manufactured at low cost. The electrode 10 mainly composed of Ni (the alloy thin plate electrode 15 having a porous structure) has a thickness in the range of 0.03 mm to 0.3 mm, so that the electric resistance of the electrode 10 is low, and the electrode 10 has a smooth proton. By using the electrode 10 for the fuel cell 20, sufficient electric power can be generated in the fuel cell 20 and sufficient electric energy can be supplied to the load connected to the fuel cell 20. By using the electrode 10 for the hydrogen gas generator 29, the electrolysis can be performed efficiently, and the hydrogen gas generator 29 can generate a sufficient hydrogen gas.

  As another example of the electrode 10 formed from a transition metal, other transitions processed into a powdered form excluding Fe powder and Fe mainly containing powdered Fe (iron) powder. Metal (powder Ti (titanium), powdery Cr (chromium), powdery Mn (manganese), powdery Co (cobalt), powdery Ni (nickel), powdery Cu (copper), A metal obtained by uniformly mixing and dispersing powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver) powders. An alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing a powder mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Fe (iron) powder is formed into a porous thin plate having a large number of fine channels 14 (passage holes), and has a thickness dimension. Is in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm. The electrode 10 mainly composed of Fe powder (the alloy thin plate electrode 15 having a porous structure) has a composite work function of the work function of Fe and the work function of at least two types of transition metals other than Fe, which is a platinum group element. Are selected from among various transition metals, at least two types of transition metal powders excluding the Fe powder. In the electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Fe powder, the transition metal powder having the lowest melting point is melted during firing of the metal powder mixture 16 compressed into a thin plate having a predetermined area. The powder of another transition metal is joined using the molten transition metal as a binder.

  In the electrode 10 containing Fe (iron) powder as a main component, the weight ratio of the powdered Fe metal powder mixture 16 to the total weight is in the range of 30% to 50%. Processed at least one transition metal (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Co (cobalt), powder Ni (nickel), Metal powder of powdered Cu (copper), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver)) The weight ratio to the total weight of the mixture 16 is in the range of 20% to 50%, and at least one other transition metal (powder Ti (titanium), powder Cr ( Chromium), powdered Mn (manganese), powdered Co (cobalt), powdered Ni (nickel) At least one of powdered Cu (copper), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), and powdered Ag (silver) )) Is in the range of 3% to 20% with respect to the total weight of the metal powder mixture 16. The weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture 16 is in the range of 3% to 20%.

  Specific examples of the electrode 10 containing Fe (iron) powder as a main component include metal powder obtained by uniformly mixing and dispersing Fe powder, Ni (nickel) powder, and Cu (copper) powder. The alloy thin plate electrode 15 having a porous structure in which a plurality of fine channels 14 (passage holes) are formed by compressing the mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a weight ratio of the Fe powder of 48% with respect to the total weight of the metal powder mixture 16, a weight ratio of the Ni powder of 48% with respect to the total weight of the metal powder mixture 16, and the metal powder mixture 16. The weight ratio of Cu powder to the total weight of 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 Cu powder is melted, and the molten Cu serves as a binder to form the Fe powder and the Ni powder. Has joined the body.

  Other specific examples of the electrode 10 containing Fe (iron) powder as a main component include a metal obtained by uniformly mixing and dispersing Fe powder, Ti (titanium) powder, and Ag (silver) powder. An alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing a powder mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a Fe powder weight ratio of 48% with respect to the total weight of the metal powder mixture 16, a Ti powder weight ratio of 46% with respect to the total weight of the metal powder mixture 16, and a metal powder mixture 16. The powder weight ratio of Ag to the total weight 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 powder is melted, and the molten Ag serves as a binder to form the Fe powder and the Ti powder. Has joined the body.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) formed of a powder of Fe as a main component and having a thickness in the range of 0.03 mm to 0.3 mm has a work function of Fe and at least two types other than Fe. At least two transition metal powders other than Fe powder are selected from various transition metals so that the work function of the transition metal and the work function of the transition metal are close to the work function of the platinum group element. Therefore, it has substantially the same work function as the platinum group element, can exhibit substantially the same catalytic activity (catalysis) as the platinum group element, and has a fuel electrode such as the fuel cell 20 and the hydrogen gas generator 29. 20, the anode 30 (anode) or the air electrode 21, and the cathode 31 (cathode) can be suitably used.

  The electrode 10 (alloy thin-plate electrode 15 having a porous structure) is formed from a powder of Fe and a powder of at least two types of transition metals other than a powder of Fe selected from various transition metals, Since expensive platinum group elements are not used, the non-platinum fuel electrode 20, anode 30, air electrode 21, and cathode 31 can be manufactured at low cost. Since the electrode 10 containing Fe as a main component (alloy thin plate electrode 15 having a porous structure) has a thickness in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode 10 is low, and protons are smoothly applied to the electrode 10. By using the electrode 10 for the fuel cell 20, sufficient electric power can be generated in the fuel cell 20 and sufficient electric energy can be supplied to the load connected to the fuel cell 20. By using the electrode 10 for the hydrogen gas generator 29, the electrolysis can be performed efficiently, and the hydrogen gas generator 29 can generate a sufficient hydrogen gas.

  As another example of the electrode 10 formed from a transition metal, other transitions processed into a powdered state excluding Cu powder and Cu as a main component are powdered Cu (copper) powder. Metal (powder Ti (titanium), powdery Cr (chromium), powdery Mn (manganese), powdery Fe (iron), powdery Co (cobalt), powdery Ni (nickel), A metal obtained by uniformly mixing and dispersing powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver) powders. An alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing a powder mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Cu (copper) powder is formed into a porous thin plate having a large number of fine channels 14 (passage holes), and has a thickness dimension. Is in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm. The electrode 10 mainly composed of Cu powder (the alloy thin plate electrode 15 having a porous structure) has a composite work function of the work function of Cu and the work function of at least two types of transition metals other than Cu, which is a platinum group element. , At least two types of transition metal powder other than the Cu powder are selected from various transition metals. In the electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Cu powder, the transition metal powder having the lowest melting point is melted during firing of the metal powder mixture 16 compressed into a thin plate having a predetermined area. The powder of another transition metal is joined using the molten transition metal as a binder.

  In the electrode 10 mainly composed of Cu (copper) powder, the weight ratio of the Cu metal powder mixture 16 processed into a powder to the total weight is in the range of 30% to 50%, Processed at least one transition metal (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Fe (iron), powder Co (cobalt), Metal powder of powdered Ni (nickel), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver)) The weight ratio to the total weight of the mixture 16 is in the range of 20% to 50%, and at least one other transition metal (powder Ti (titanium), powder Cr ( Chromium), powdered Mn (manganese), powdered Fe (iron), powdered Co (cobalt) Powdered Ni (nickel), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver), and at least one other metal) The weight ratio of the powder mixture 16 to the total weight is in the range of 3% to 20%. The weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture 16 is in the range of 3% to 20%.

  Specific examples of the electrode 10 mainly composed of Cu (copper) powder include metal powder obtained by uniformly mixing and dispersing Cu powder, Fe (iron) powder, and Zn (zinc) powder. The alloy thin plate electrode 15 having a porous structure in which a plurality of fine channels 14 (passage holes) are formed by compressing the mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a Cu powder weight ratio of 48% with respect to the total weight of the metal powder mixture 16, a Fe powder weight ratio of 48% with respect to the total weight of the metal powder mixture 16, The powder weight ratio of Zn to the total weight is 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 Zn powder is melted, and the molten Zn serves as a binder to form the Cu powder and Fe. And powder.

  Specific examples of the electrode 10 mainly containing Cu (copper) powder include metal powder obtained by uniformly mixing and dispersing Cu powder, Fe (iron) powder, and Ag (silver) powder. The alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing the mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a Cu powder weight ratio of 48% with respect to the total weight of the metal powder mixture 16, a Fe powder weight ratio of 46% with respect to the total weight of the metal powder mixture 16, and a metal powder mixture 8 of The powder weight ratio of Ag to the total weight 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 powder is melted, and the molten Ag serves as a binder to form the Cu powder and Fe. And powder.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) formed of a Cu powder as a main component and having a thickness in the range of 0.03 mm to 0.3 mm has a work function of Cu and at least two types other than Cu. At least two other transition metal powders except for the Cu powder are selected from various transition metals so that the work function of the transition metal and the work function of the transition metal are close to the work function of the platinum group element. Therefore, it has substantially the same work function as the platinum group element, can exhibit substantially the same catalytic activity (catalysis) as the platinum group element, and has a fuel electrode such as the fuel cell 20 and the hydrogen gas generator 29. 20, the anode 30 (anode) or the air electrode 21, and the cathode 31 (cathode) can be suitably used.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) is formed from a powder of Cu and a powder of at least two types of transition metals other than a powder of Cu selected from various transition metals, Since expensive platinum group elements are not used, the non-platinum fuel electrode 20, anode 30, air electrode 21, and cathode 31 can be manufactured at low cost. Since the electrode 10 mainly composed of Cu (alloy thin plate electrode 15 having a porous structure) has a thickness in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode is low, and protons move smoothly through the electrode. By using the electrode 10 for the fuel cell 20, sufficient electricity can be generated in the fuel cell 20 and sufficient electric energy can be supplied to the load connected to the fuel cell 20. At the same time, by using the electrode 10 for the hydrogen gas generator 29, electrolysis can be performed efficiently, and the hydrogen gas generator 29 can generate sufficient hydrogen gas.

  FIG. 10 is a diagram illustrating a method for manufacturing the electrode 10. As shown in FIG. 10, the electrode 10 is manufactured by an electrode manufacturing method including a transition metal selection step S1, a metal powder mixture creation step S2, a metal sheet creation step S3, and a porous structure alloy sheet electrode creation step S4. In the transition metal selection step S1, the various transition metals 36 are selected from various transition metals 36 such that the composite work function of the work functions of at least three types of transition metals 36 selected from the various transition metals 36 is close to the work function of the platinum group element. At least three types of transition metals 36 (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 electrode 10 mainly containing Ni (nickel), Cu (copper) and ZN (zinc) are selected, or Mn (manganese) and Mo (molybdenum) are used. Select For the electrode 10 mainly containing Fe (iron), Ni (nickel) and Cu (copper) are selected, or Ti (titanium) and Ag (silver) are selected. For the electrode 10 mainly containing Cu (copper), Fe (iron) and Zn (zinc) are selected, or Fe (iron) and Ag (silver) are selected.

  In the metal powder mixture preparation step S2, a metal powder mixture 16 is prepared by uniformly mixing and dispersing powders of at least three types of transition metals 36 selected in the transition metal selection step S1. In the metal powder mixture forming step S2, in the electrode 10 containing Ni (nickel) as a main component, each of Ni, Cu (copper) and ZN (zinc) selected in the transition metal selecting step S1 is 10 μm by a pulverizer. Finely pulverized to a particle size of ~ 200 µm to produce Ni powder, Cu powder and Zn powder. Next, Ni powder, Cu powder, and Zn powder are put into a mixer, and the Ni powder, Cu powder, and Zn powder are stirred and mixed by the mixer, and the Ni powder is mixed. A metal powder mixture 16 in which the powder, Cu powder and Zn powder are uniformly mixed and dispersed is produced. Alternatively, each of Ni (nickel), Mn (manganese), and Mo (molybdenum) 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 to obtain a Ni powder, Mn powder. Powder and Mo powder are prepared. Next, Ni powder, Mn powder, and Mo powder are put into a mixer, and the Ni powder, Mn powder, and Mo powder are stirred and mixed by the mixer, and the Ni powder is mixed. A metal powder mixture 16 in which powder, Mn powder, and Mo powder are uniformly mixed and dispersed is produced.

  In the metal powder mixture preparation step S2, in the electrode 10 containing Fe (iron) as a main component, each of Fe, Ni (nickel), and Cu (copper) selected in the transition metal selection step S1 was reduced to 10 μm by a pulverizer. Finely pulverized to a particle size of ~ 200 µm to produce Fe powder, Ni powder and Cu powder. Next, the Fe powder, the Ni powder, and the Cu powder are put into a mixer, and the Fe powder, the Ni powder, and the Cu powder are stirred and mixed by the mixer, and the Fe powder is mixed. A metal powder mixture 16 is prepared in which the powder, Ni powder and Cu powder 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 to obtain a powder of Fe, Powder and Ag powder are prepared. Next, the Fe powder, the Ti powder, and the Ag powder are put into a mixer, and the Fe powder, the Ti powder, and the Ag powder are stirred and mixed by the mixer, and the Fe powder is mixed. A metal powder mixture 16 in which the powder, Ti powder and Ag powder are uniformly mixed and dispersed is produced.

  In the metal powder mixture preparation step S2, in the electrode 10 containing Cu (copper) as a main component, each of Cu, Fe (iron) and Zn (zinc) selected in the transition metal selection step S1 is reduced to 10 μm by a pulverizer. Finely pulverized to a particle size of ~ 200 µm to produce Cu powder, Fe powder and Zn powder. Next, Cu powder, Fe powder, and Zn powder are put into a mixer, and the Cu powder, Fe powder, and Zn powder are stirred and mixed by the mixer, and the Cu powder is mixed. A metal powder mixture 16 in which powder, Fe powder, and Zn powder 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 size of 10 μm to 200 μm by a fine pulverizer, and Cu powder, Fe powder Powder and Ag powder are prepared. Next, the Cu powder, the Fe powder, and the Ag powder are put into a mixer, and the Cu powder, the Fe powder, and the Ag powder are stirred and mixed by the mixer, and the Cu powder is mixed. A metal powder mixture 16 in which powder, Fe powder and Ag powder are uniformly mixed and dispersed is produced.

  In the metal sheet forming step S3, the metal powder mixture 16 formed in the metal powder mixture forming step S2 is pressurized at a predetermined pressure, and the metal powder mixture 16 is compressed into a sheet having a predetermined area to form a metal sheet 11. In the metal sheet making step S3, the metal powder mixture 16 is put into a mold, and the metal sheet 11 is made by press working in which the mold is pressed (pressed) by a press machine. The press pressure (pressure) at the time of press working is in the range of 500 MPa to 800 MPa. When the pressing pressure (pressure) is less than 500 MPa, the opening area (opening diameter) of the flow path 14 (passage hole) formed in the metal thin plate 11 increases, and the thickness of the metal thin plate 11 is reduced to 0.03 mm to 0.3 mm. On the other hand, a large number of fine channels 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm cannot be formed in the metal sheet 11. If the pressing pressure (pressure) exceeds 800 MPa, the opening area (opening diameter) of the flow path 14 (passage hole) formed in the metal thin plate 11 becomes unnecessarily small, and the thickness of the metal thin plate 11 becomes 0.03 mm or more. A large number of fine flow paths 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm cannot be formed in the metal thin plate 11 while the diameter is set to 0.3 mm. In the electrode manufacturing method, the metal powder mixture 16 is pressurized (compressed) at a pressure in the above range, so that the thickness of the metal thin plate 11 is 0.03 mm to 0.3 mm and the opening diameter is in the range of 1 μm to 100 μm. The metal sheet 11 having a large number of fine channels 14 (passage holes) can be formed.

  In the metal thin plate forming step S3, in the electrode 10 containing Ni (nickel) as a main component, a predetermined amount of a metal powder mixture 16 obtained by mixing Ni powder, Cu (copper) powder, and ZN (zinc) powder. Is put into a mold, the metal powder mixture 16 is pressed (compressed) by press working to compress the metal powder mixture 16 into a thin plate having a predetermined area, and has a thickness of 0.03 mm to 0.3 mm. Then, a metal sheet 11 having a large number of fine channels 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm is produced. Alternatively, a predetermined amount of a metal powder mixture 16 obtained by mixing Ni powder, Mn (manganese) powder, and Mo (molybdenum) powder is charged into a mold, and the metal powder mixture 16 is pressed. The metal powder mixture 16 is compressed into a thin plate having a predetermined area by pressurization (compression), and a large number of fine channels having a thickness of 0.03 mm to 0.3 mm and an opening diameter of 1 μm to 100 μm. The metal sheet 11 having the holes 14 (passage holes) is formed.

  In the metal thin plate forming step S3, the electrode 10 containing Fe (iron) as a main component has a metal powder mixture 16 obtained by mixing Fe powder, Ni (nickel) powder, and Cu (copper) powder. The fixed amount is put into a mold, and the metal powder mixture 16 is pressed (compressed) by pressing to compress the metal powder mixture 16 into a thin plate having a predetermined area, and the thickness dimension is 0.03 mm to 0.3 mm. Then, the metal sheet 11 having a large number of fine channels 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm is formed. Alternatively, a predetermined amount of a metal powder mixture 16 obtained by mixing Fe powder, Ti (titanium) powder, and Ag (silver) powder is charged into a mold, and the metal powder mixture 16 is pressed. The metal powder mixture 16 is compressed into a thin plate having a predetermined area by pressurization (compression), and a large number of fine channels having a thickness of 0.03 mm to 0.3 mm and an opening diameter of 1 μm to 100 μm. The metal sheet 11 having the holes 14 (passage holes) is formed.

  In the metal thin plate forming step S3, the electrode 10 containing Cu (copper) as a main component has a metal powder mixture 16 obtained by mixing Cu powder, Fe (iron) powder, and Zn (zinc) powder. The fixed amount is put into a mold, and the metal powder mixture 16 is pressed (compressed) by pressing to compress the metal powder mixture 16 into a thin plate having a predetermined area, and the thickness dimension is 0.03 mm to 0.3 mm. Then, the metal sheet 11 having a large number of fine channels 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm is formed. Alternatively, a predetermined amount of a metal powder mixture 16 in which Cu powder, Fe (iron) powder, and Ag (silver) powder are mixed is put into a mold, and the metal powder mixture 16 is pressed. The metal powder mixture 16 is compressed into a thin plate having a predetermined area by pressurization (compression), and a large number of fine channels having a thickness of 0.03 mm to 0.3 mm and an opening diameter of 1 μm to 100 μm. The metal sheet 11 having the holes 14 (passage holes) is formed.

  In the porous structure alloy thin plate electrode forming step S4, the metal thin plate 11 formed in the metal thin plate forming step S3 is put into a furnace (electric furnace), and the metal thin plate 11 is fired (sintered) at a predetermined temperature in the furnace to obtain a large number of pieces. An alloy thin plate electrode 15 (electrode 10) having a porous structure in which fine channels 14 (passage holes) are formed is produced. In the porous structure alloy sheet electrode forming step S4, the metal sheet 11 is held for a long time at a temperature at which the powder of the transition metal 36 having the lowest melting point among the at least three types of transition metals 36 selected in the transition metal selection step S3 is melted. Bake. The firing (sintering) time is 3 hours to 6 hours. In the porous structure alloy thin plate electrode forming step S4, the powder of the transition metal 36 having the lowest melting point is melted during firing of the thin metal plate 11 (metal powder mixture 16) compressed into a thin plate having a predetermined area, and the melted transition metal is melted. Using the metal 36 as a binder, the powder of another transition metal 36 is joined (fixed).

  In the porous alloy thin plate electrode forming step S4, in the electrode 10 containing Ni (nickel) as a main component, a metal powder mixture 16 obtained by mixing Ni powder, Cu (copper) powder, and ZN (zinc) powder is used. Is compressed in a furnace (electric furnace) for a long time to form an alloy thin plate electrode 15 (electrode having a porous structure) in which a large number of fine channels 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. Make 10). In the metal sheet 11 formed of Ni powder, Cu powder, and Zn powder, the metal sheet 11 was fired and melted at a temperature (for example, 500 ° C. to 800 ° C.) at which the Zn powder was melted. The Ni powder and the Cu powder are joined (fixed) by the Zn powder.

  In the electrode 10 containing Ni (nickel) as a main component, the metal thin plate 11 obtained by compressing a metal powder mixture 16 obtained by mixing Ni powder, Mn (manganese) powder, and Mo (molybdenum) powder is used. Baking is performed in a furnace (electric furnace) for a long time to form an alloy thin plate electrode 15 (electrode 10) having a porous structure in which a large number of fine flow paths 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. In the metal sheet 11 formed from Ni powder, Mn powder, and Mo powder, the metal sheet 11 was fired and melted at a temperature at which the Mn powder was melted (for example, 1200 ° C. to 1400 ° C.). The Mn powder and the Mo powder are joined (fixed) by the Mn powder.

  In the porous structure alloy thin plate electrode forming step S4, in the electrode 10 containing Fe (iron) as a main component, a metal powder mixture obtained by mixing Fe powder, Ni (nickel) powder, and Cu (copper) powder 16 is sintered in a furnace (electric furnace) for a long time, and an alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm is formed. An electrode 10) is made. In the metal sheet 11 formed from the powder of Fe, the powder of Ni, and the powder of Cu, the metal sheet 11 was baked at a temperature at which the powder of Cu was melted (for example, 1100 ° C. to 1300 ° C.) and melted. The Fe powder and the Ni powder are joined (fixed) by the Cu powder.

  Further, in the electrode 10 containing Fe (iron) as a main component, the metal thin plate 11 obtained by compressing a metal powder mixture 16 obtained by mixing Fe powder, Ti (titanium) powder, and Ag (silver) powder is used. Baking is performed in a furnace (electric furnace) for a long time to form an alloy thin plate electrode 15 (electrode 10) having a porous structure in which a large number of fine flow paths 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. In the metal sheet 11 formed from the powder of Fe, the powder of Ti, and the powder of Ag, the metal sheet 11 is baked and melted at a temperature at which the Ag powder is melted (for example, 1000 ° C. to 1200 ° C.). The Ag powder joins (fixes) the Fe powder and the Ti powder.

  In the porous structure alloy thin plate electrode forming step S4, in the electrode 10 containing Cu (copper) as a main component, a metal powder mixture obtained by mixing Cu powder, Fe (iron) powder, and Zn (zinc) powder. 16 is sintered in a furnace (electric furnace) for a long time, and an alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm is formed. An electrode 10) is made. In the metal sheet 11 formed of Cu powder, Fe powder, and Zn powder, the metal sheet 11 was fired and melted at a temperature at which the Zn powder was melted (for example, 500 ° C. to 800 ° C.). The Cu powder and the Fe powder are joined (fixed) by the Zn powder.

  In the electrode 10 containing Cu (copper) as a main component, the metal thin plate 11 obtained by compressing a metal powder mixture 16 obtained by mixing Cu powder, Fe (iron) powder, and Ag (silver) powder is used. Baking is performed in a furnace (electric furnace) for a long time to form an alloy thin plate electrode 15 (electrode 10) having a porous structure in which a large number of fine flow paths 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. In the metal sheet 11 formed of Cu powder, Fe powder, and Ag powder, the metal sheet 11 was fired and melted at a temperature at which the Ag powder was melted (for example, 1000 ° C. to 1100 ° C.). The Cu powder and the Fe powder are bonded (fixed) by the Ag powder.

  The electrode manufacturing method is such that the thickness dimension L1 is in the range of 0.03 mm to 0.3 mm by the transition metal selection step S1, the metal powder mixture creation step S2, the metal sheet creation step S3, and the porous structure alloy sheet electrode creation step S4. The electrode 10 having a large number of fine channels 14 (passage holes) can be formed, and the non-platinum fuel electrode 20, anode 30, air electrode 21, and cathode 31 that do not use platinum group elements can be manufactured at low cost. Non-platinum which can utilize the catalytic function sufficiently and reliably and has catalytic activity (catalytic activity) and can be used as the fuel electrode 20, the anode 30, the air electrode 21, and the cathode 31 Electrode 10 can be made.

  According to the electrode manufacturing method, the electrode 10 having a thickness in the range of 0.03 mm to 0.3 mm and having many fine channels 14 (passage holes) can be formed. And the protons can move smoothly through the electrode 10, generating sufficient electricity in the fuel cell 20 and supplying sufficient electric energy to the load 28 connected to the fuel cell 20. An electrode 10 that can be supplied can be made. According to the electrode manufacturing method, the electrolysis can be efficiently performed in the hydrogen gas generator 29, and the electrode 10 capable of generating sufficient hydrogen gas in the hydrogen gas generator 29 can be manufactured.

DESCRIPTION OF SYMBOLS 10 Electrode 11 Metal thin plate 12 Front surface 13 Rear surface 14 Channel (passage hole)
Reference Signs List 15 Alloy thin plate electrode having porous structure 16 Metal powder mixture 17 Flow opening 18 Outer rim 19 Cell 20 Fuel cell 21 Fuel electrode 22 Air electrode 23 Solid polymer electrolyte membrane 24a, b Separator (bipolar plate)
25a, b Gas diffusion layer 26a, b Gas seal 27 Conductor 28 Load 29 Hydrogen gas generator 30 Anode 31 Cathode 32 Solid polymer electrolyte membrane 33a Anode power supply member 33b Cathode power supply member 34a Positive reservoir 34b Positive reservoir 35a Positive Main electrode 35b Cathode main electrode 36 Transition metal

  The present invention relates to an electrode used as an anode or a cathode.

  There is disclosed a fuel cell electrode including a platinum catalyst in which platinum is supported on nitrogen-doped carbon obtained by calcining a porous metal complex (PCP / MOF) containing zinc as a low boiling point metal (see Patent Document 1). Since this fuel cell electrode uses a porous metal complex (PCP / MOF) containing zinc, which is a low boiling point metal, as a raw material for production, the catalyst carrier is an NDC having a large specific surface area with almost no metal derived from the raw material. And a highly active platinum catalyst can be obtained by supporting a small amount of platinum. Further, since no metal derived from a porous metal complex (PCP / MOF), which is a production raw material, is contained, firing conditions can be freely set. That is, it is possible to control the nitrogen content and crystallinity in the obtained NDC by changing the organic compound linker of the porous metal complex (PCP / MOF) used as a raw material and adjusting the firing temperature.

JP 2018-23929 A

  Various platinum-supporting 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 suppress the amount of the platinum group element used. Further, development of inexpensive electrodes having a non-platinum catalyst using a metal 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 an electrode which can be manufactured at low cost without using a platinum group element, has catalytic activity (catalytic action), and can be used as an anode or a cathode. Another object of the present invention is to enable a fuel cell to generate sufficient electricity, supply sufficient electric energy to a load connected to the fuel cell, and efficiently perform electrolysis in a hydrogen gas generator. An object of the present invention is to provide an electrode which can be performed well and can generate a sufficient amount of hydrogen gas.

  The premise of the present invention for solving the above problems is an electrode used as an anode or a cathode.

  The feature of the present invention on the above premise is that the electrode is formed of at least three types of transition metals selected from various transition metals, and powders of at least three types of the selected transition metals are uniformly mixed and dispersed. A porous alloy thin plate electrode in which a metal powder mixture is compressed into a thin plate having a predetermined area and then fired to form a large number of fine channels, and the thickness of the porous thin alloy electrode is 0.03 mm to 0 mm. In the case of an alloy thin-plate electrode having a porous structure in the range of 0.3 mm, the work function of at least three kinds of selected transition metals is selected from various transition metals so that the work function thereof approximates the work function of the platinum group element. From at least three types of transition metals.

  As an example of the present invention, an alloy thin plate electrode having a porous structure is formed by using a Ni powder as a main component and having a thickness in a range of 0.03 mm to 0.3 mm. In order to make the work function of the function and the work function of at least two types of transition metals other than Ni close to the work function of the platinum group element, at least other types of transition metal excluding Ni powder from various transition metals are used. Two transition metal powders were selected.

  As another example of the present invention, the weight ratio of the Ni powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the metal of one type of transition metal powder excluding the Ni powder is used. The weight ratio of the powder mixture to the total weight of the powder mixture is in the range of 20% to 50%, and the weight ratio of at least one transition metal powder other than the Ni powder to the total weight of the metal powder mixture is , In the range of 3% to 20%.

  As another example of the present invention, an alloy thin plate electrode having a porous structure is formed by using a powder of Fe as a main component and having a thickness in the range of 0.03 mm to 0.3 mm. In addition to removing Fe powder from various transition metals, the composite work function of the work function of the transition metal and the work function of at least two other transition metals other than Fe approximates the work function of the platinum group element. Of at least two types of transition metals are selected.

  As another example of the present invention, the weight ratio of the Fe powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the metal of one type of transition metal powder excluding the Fe powder is used. The weight ratio with respect to the total weight of the powder mixture is in the range of 20% to 50%, and the weight ratio of the powder of at least one other transition metal excluding the powder of Fe to the total weight of the metal powder mixture is , In the range of 3% to 20%.

  As another example of the present invention, an alloy thin plate electrode having a porous structure is formed by using a Cu powder as a main component and having a thickness in a range of 0.03 mm to 0.3 mm. In addition to removing Cu powder from various transition metals, the composite work function of the work function of the transition metal and the work function of at least two other transition metals other than Cu approximates the work function of the platinum group element. Of at least two types of transition metals are selected.

  As another example of the present invention, the weight ratio of the Cu powder to the total weight of the metal powder mixture is in a range of 30% to 50%, and the metal of one type of transition metal powder excluding the Cu powder is used. The weight ratio with respect to the total weight of the powder mixture is in the range of 20% to 50%, and the weight ratio of the powder of at least one other transition metal excluding the Cu powder to the total weight of the metal powder mixture is , In the range of 3% to 20%.

  As another example of the present invention, the porosity of the porous alloy thin plate electrode is in the range of 15% to 30%.

As another example of the present invention, the density of the alloy thin electrodes of porous structure ^is in the range of ^{5.0g / cm 2 ~7.0g / cm 2} .

  As another example of the present invention, the particle size of the transition metal powder is in the range of 10 μm to 200 μm.

  As another example of the present invention, in the case of an alloy thin plate electrode having a porous structure, the powder of the transition metal having the lowest melting point is melted during firing of a metal powder mixture compressed into a thin plate having a predetermined area, and the melted transition metal is bound with a binder. As another transition metal powder.

  As another example of the present invention, the weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture is in the range of 3% to 20%.

  As another example of the present invention, the electrode is formed of various transition metals such that the composite work function of the work functions of at least three transition metals selected from various transition metals is close to the work function of the platinum group element. A transition metal selection step of selecting at least three types of transition metals from among them, and a metal powder for producing a metal powder mixture in which at least three types of transition metal powders selected by the transition metal selection step are uniformly mixed and dispersed. A mixture preparation step, a metal sheet preparation step of pressing the metal powder mixture produced by the metal powder mixture preparation step at a predetermined pressure to produce a metal sheet, and a metal sheet produced by the metal sheet preparation step at a predetermined temperature. It is manufactured by a porous alloy thin plate electrode forming step of firing to form a porous alloy thin plate electrode in which a large number of fine channels are formed.

  As another example of the present invention, in the metal powder mixture preparation step, at least three types of transition metals selected in the transition metal selection step are finely pulverized to a particle size of 10 μm to 200 μm.

  As another example of the present invention, the metal sheet preparing step includes pressing the metal powder mixture produced by the metal powder mixture producing step at a pressure of 500 MPa to 800 MPa to reduce the thickness dimension of 0.03 mm to 0.3 mm. A thin metal plate having a large number of fine channels is prepared.

  As another example of the present invention, the step of forming a porous alloy thin plate electrode includes a step of melting a metal of a transition metal powder having a lowest melting point among at least three types of transition metals selected in the transition metal selection step. The thin plate is fired.

  ADVANTAGE OF THE INVENTION According to the electrode which concerns on this invention, it is formed from at least 3 types of transition metals selected from various transition metals, and the metal which mixed and dispersed the powder of at least 3 types of these selected transition metals uniformly. An alloy thin plate electrode having a porous structure in which a powder mixture is compressed into a thin plate having a predetermined area and then fired to form a large number of fine channels (passage holes). The work function of at least three selected transition metals is selected. Since at least three transition metals are selected from various transition metals so that the composite work function of the platinum group element is close to the work function of the platinum group element, the transition metal has a work function that is substantially the same as that of the platinum group element. It can exhibit substantially the same catalytic activity (catalysis) as the group element, and can be suitably used as an anode or a cathode of a fuel cell, a hydrogen gas generator, or the like. The electrode is formed from at least three transition metals selected from various transition metals, does not utilize expensive platinum group elements, and can make non-platinum anodes or cathodes inexpensive. Since the electrode has a porous alloy thin plate electrode having a thickness in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode is low, protons can move smoothly through the electrode, and the electrode can be used in a fuel cell. By using, sufficient electricity can be generated in the fuel cell, sufficient electrical energy can be supplied to the load connected to the fuel cell, and by using the electrode in the hydrogen gas generator, Electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated.

  An alloy thin plate electrode having a porous structure is formed by using Ni powder as a main component and having a thickness in the range of 0.03 mm to 0.3 mm, and has a work function of Ni and a work function of at least two types of transition metals other than Ni. The electrode in which at least two types of transition metal powders other than Ni powder are selected from various transition metals so that the composite work function thereof is close to the work function of the platinum group element, Excluding Ni powder from various transition metals so that the composite work function of the work function of Ni and the work function of at least two other transition metals other than Ni approximates the work function of a platinum group element. Since at least two types of transition metal powders are selected, they have substantially the same work function as the platinum group element, and can exhibit almost the same catalytic activity (catalysis) as the platinum group element, Fuel cell and hydrogen gas generator It can be suitably used as an anode or cathode and the like. The electrode is formed of Ni powder and at least two types of transition metal powder other than Ni powder selected from various transition metals, and expensive platinum group elements are used. In addition, a non-platinum anode or cathode can be manufactured at low cost. Since the thickness of the electrode of the alloy thin plate having a porous structure containing Ni as a main component is in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode is low, and protons can move smoothly through the electrode. By using the electrode in the fuel cell, sufficient electricity can be generated in the fuel cell, sufficient electric energy can be supplied to the load connected to the fuel cell, and the electrode can be used as a hydrogen gas generator. In this case, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated.

  The weight ratio of the Ni powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the weight ratio of one transition metal powder excluding the Ni powder to the total weight of the metal powder mixture is The electrode in the range of 20% to 50% and the weight ratio of the powder of at least one other transition metal excluding the Ni powder to the total weight of the metal powder mixture in the range of 3% to 20% is , Ni powder is selected from various transition metals so that a composite work function of a work function of Ni and a work function of at least two types of transition metals other than Ni approximates a work function of a platinum group element. At least two other transition metal powders are selected, and the weight ratio of the Ni powder, the weight ratio of at least one transition metal powder excluding the Ni powder, and the Ni powder The weight ratio of at least one other transition metal powder excluding By setting it within the range, it has a work function substantially the same as that of the platinum group element, and can exhibit substantially the same catalytic activity (catalysis) as the platinum group element. It can be suitably used. The electrode is formed from the powder of Ni in the above weight ratio and the powder of at least two kinds of transition metals in the above weight ratio excluding Ni selected from various transition metals, and an expensive platinum group element is used. In addition, a non-platinum anode or cathode can be produced at low cost.

  An alloy thin plate electrode having a porous structure is formed to have a thickness of 0.03 mm to 0.3 mm with Fe powder as a main component, and has a work function of Fe and a work function of at least two types of transition metals other than Fe. An electrode in which at least two types of transition metal powders other than Fe powders are selected from various transition metals so that the composite work function thereof is close to the work function of the platinum group element, Excluding Fe powder from various transition metals so that the composite work function of the work function of Fe and the work function of at least two other transition metals other than Fe approximates the work function of a platinum group element. Since at least two types of transition metal powders are selected, they have substantially the same work function as the platinum group element, and can exhibit almost the same catalytic activity (catalysis) as the platinum group element, Fuel cell and hydrogen gas generator It can be suitably used as an anode or cathode and the like. The electrode is made of Fe powder and at least two kinds of transition metal powders other than Fe powder selected from various transition metals, and expensive platinum group elements are used. In addition, a non-platinum anode or cathode can be manufactured at low cost. The electrode has a porous alloy thin plate electrode containing Fe as a main component, and the thickness of the electrode is in the range of 0.03 mm to 0.3 mm. Therefore, the electric resistance of the electrode is low, and protons can move smoothly through the electrode. By using the electrode in the fuel cell, sufficient electricity can be generated in the fuel cell, sufficient electric energy can be supplied to the load connected to the fuel cell, and the electrode can be used as a hydrogen gas generator. In this case, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated.

  The weight ratio of the Fe powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the weight ratio of one transition metal powder excluding the Fe powder to the total weight of the metal powder mixture. Wherein the weight ratio of at least one transition metal powder other than Fe powder to the total weight of the metal powder mixture is in the range of 3% to 20%. Is a powder of Fe from various transition metals so that 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 approximates the work function of a platinum group element. And at least two types of transition metal powders except for the Fe powder, the weight ratio of the Fe powder, the weight ratio of at least one transition metal powder excluding the Fe powder, and the Fe powder Weight ratio of powder of at least one other transition metal excluding body When the content is within the above range, the catalyst has substantially the same work function as the platinum group element, and can exhibit substantially the same catalytic activity (catalysis) as the platinum group element. It can be suitably used as a cathode. The electrode is formed from the powder of Fe in the weight ratio and the powder of at least two types of transition metals in the weight ratio excluding Fe selected from various transition metals, and an expensive platinum group element is used. In addition, a non-platinum anode or cathode can be produced at low cost.

  An alloy thin plate electrode having a porous structure is formed by using a Cu powder as a main component to a thickness of 0.03 mm to 0.3 mm, and has a work function of Cu and a work function of at least two types of transition metals other than Cu. An electrode in which at least two types of transition metal powders other than the Cu powder are selected from various transition metals so that the composite work function thereof is close to the work function of the platinum group element, Excluding Cu powder from various transition metals so that the composite work function of the work function of Cu and the work function of at least two other transition metals other than Cu approximates the work function of a platinum group element. Since at least two types of transition metal powders are selected, they have substantially the same work function as the platinum group element, and can exhibit almost the same catalytic activity (catalysis) as the platinum group element, Fuel cell and hydrogen gas generator It can be suitably used as an anode or cathode and the like. The electrode is formed of a powder of Cu and at least two types of transition metal powder other than a powder of Cu selected from various transition metals, and uses an expensive platinum group element. In addition, a non-platinum anode or cathode can be manufactured at low cost. Since the thickness of the electrode of the alloy thin plate electrode having a porous structure containing Cu as a main component is in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode is low, and protons can move smoothly through the electrode. By using the electrode in the fuel cell, sufficient electricity can be generated in the fuel cell, sufficient electric energy can be supplied to the load connected to the fuel cell, and the electrode can be used as a hydrogen gas generator. In this case, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated.

  The weight ratio of the Cu powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the weight ratio of one transition metal powder excluding the Cu powder to the total weight of the metal powder mixture is The electrode in the range of 20% to 50% and the weight ratio of the powder of at least one other transition metal excluding the powder of Cu to the total weight of the metal powder mixture in the range of 3% to 20% A Cu powder is selected from various transition metals so that a composite work function of a work function of Cu and a work function of at least two types of transition metals other than Cu approximates a work function of a platinum group element. At least two other transition metal powders are selected, and the weight ratio of the Cu powder, the weight ratio of at least one transition metal powder excluding the Cu powder, and the Cu powder The weight ratio of at least one other transition metal powder excluding Within this range, the catalyst has a work function substantially the same as that of the platinum group element, and can exhibit substantially the same catalytic activity (catalysis) as that of the platinum group element. The anode or cathode of a fuel cell, a hydrogen gas generator, etc. Can be suitably used. The electrode is formed from the above-mentioned weight ratio of Cu powder and at least two kinds of transition metal powder of the above-mentioned weight ratio excluding Cu selected from various transition metals, and an expensive platinum group element is used. In addition, a non-platinum anode or cathode can be produced at low cost.

  When the porosity of the porous alloy thin plate electrode is in the range of 15% to 30%, by setting the porosity of the alloy thin plate electrode in the above range, the porous thin alloy plate electrode can have a large number of fine channels ( (Porous holes), which can increase the specific surface area of the alloy thin plate electrode, and allow the gas or liquid to flow through these flow paths to make the gas or liquid contact the contact surface of the alloy thin plate electrode widely. And the catalyst activity (catalytic action) substantially similar to that of the platinum group element can be surely exhibited. The electrode can use its catalytic function sufficiently and reliably and can be suitably used as a non-platinum anode or cathode having catalytic activity (catalytic activity).

Electrode density of alloy thin electrodes of porous structure is in the range of 5.0g ^/ cm ² ~7.0g / cm 2, by making the density of the alloy sheet electrode on the range, alloy thin electrodes of porous structure are many Is formed into a porous material having fine flow passages (passage holes), and the specific surface area of the alloy thin plate electrode can be increased. The gas or liquid flows through those flow passages while the gas or liquid contacts the alloy thin plate electrode. Thus, the catalyst can be brought into wide contact with the surface, and the catalyst activity (catalysis) substantially similar to that of the platinum group element can be surely exhibited. The electrode can utilize its catalytic function sufficiently and reliably and can be suitably used as a non-platinum anode or cathode having catalytic activity (catalytic activity).

  In an electrode in which the particle diameter of the transition metal powder is in the range of 10 μm to 200 μm, by setting the particle diameter of the transition metal in the above range, the alloy thin plate electrode having the porous structure can form a large number of fine channels (passage holes). It is possible to increase the specific surface area of the alloy thin plate electrode, and it is possible to make the gas and liquid flow widely through the flow path of the alloy thin plate electrode and the contact surface of the alloy thin plate electrode, The catalyst activity (catalysis) substantially similar to that of the platinum group element can be surely exhibited. The electrode can use its catalytic function sufficiently and reliably and can be suitably used as a non-platinum anode or cathode having catalytic activity (catalytic activity).

  The electrode in which the transition metal powder having the lowest melting point is melted during firing of the metal powder mixture compressed into a thin plate having a predetermined area, and the other transition metal powder is joined using the molten transition metal as a binder, By joining the other powdery metal with the powdery metal having the lowest melting point as a binder, the electrode has a high strength and can maintain its shape, and the electrode when the electrode is impacted Can be prevented from being damaged or damaged. Since the electrode can maintain its shape, it is possible to use its catalytic function sufficiently and reliably, and it is preferable to use it suitably as a non-platinum anode or cathode having catalytic activity (catalytic activity). it can.

  The electrode in which the weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture is in the range of 3% to 20% is such that the weight ratio of the transition metal powder serving as the binder is in the above range. Even if the transition metal serving as the binder is melted, the fine flow path (passage hole) of the porous alloy thin plate electrode is not blocked, and the porous structure of the alloy thin plate electrode can be maintained. The catalyst function can be used sufficiently and reliably, and it can be suitably used as a non-platinum anode or cathode having catalytic activity (catalysis).

  A transition that selects at least three types of transition metals from various types of transition metals so that a work function of at least three types of transition metals selected from various types of transition metals is close to the work function of a platinum group element. A metal selection step, a metal powder mixture creation step of uniformly mixing and dispersing at least three types of transition metal powders selected in the transition metal selection step, and a metal powder mixture creation step. A step of forming a metal sheet by pressing the prepared metal powder mixture at a predetermined pressure to form a metal sheet, and firing the metal sheet formed by the metal sheet preparation step at a predetermined temperature to form a large number of fine channels (passage holes). The electrode manufactured by the porous alloy thin plate electrode forming process of forming a porous alloy thin plate electrode having the above-mentioned) is formed by a transition metal selecting process or a metal powder mixture forming process. In this way, a non-platinum electrode that does not use a platinum group element can be produced at a low cost by the metal thin plate manufacturing process and the porous structure thin metal plate electrode manufacturing process, and the catalytic function can be sufficiently and reliably used, and the catalytic activity can be improved. A non-platinum electrode that has (catalytic action) and can be used as an anode or a cathode can be produced.

  The electrode for pulverizing at least three types of transition metals selected by the transition metal selection step in the metal powder mixture preparation step into particles having a particle size of 10 μm to 200 μm, by pulverizing the transition metal to a particle diameter in the above range, A porous alloy thin plate electrode having a large specific surface area can be manufactured by molding into a porous material having a large number of fine channels (passage holes), and the gas or liquid flows through these channels to form an alloy. This makes it possible to widely contact the contact surface of the thin plate electrode, and it is possible to produce an electrode capable of reliably exhibiting substantially the same catalytic activity (catalytic action) as a platinum group element. The electrode is capable of fully and reliably utilizing its catalytic function, has a catalytic activity (catalytic action), and forms a non-platinum porous alloy thin plate electrode which can be used as an anode or a cathode. be able to.

  The thin metal plate making step presses the metal powder mixture produced by the metal powder mixture producing step at a pressure of 500 Mpa to 800 Mpa to form a large number of fine channels having a thickness of 0.03 mm to 0.3 mm. The electrode for forming the formed metal thin plate is formed by pressing (compressing) the metal powder mixture at a pressure in the above-mentioned range, and having a thickness of 0.03 mm to 0.3 mm and a large number of fine channels (passage holes). ), And an alloy thin plate electrode having a non-platinum porous structure without using a platinum group element can be manufactured at a low cost. The electrode is capable of fully and reliably utilizing its catalytic function, has a catalytic activity (catalytic action), and forms a non-platinum porous alloy thin plate electrode which can be used as an anode or a cathode. be able to. The electrode has a thickness in the range of 0.03 mm to 0.3 mm, and by forming a large number of fine channels (passage holes), the electric resistance of the electrode can be reduced, and the electrode can be formed by protons. Can move smoothly, and by using the electrodes in the fuel cell, it is possible to generate sufficient electricity in the fuel cell and supply sufficient electric energy to the load connected to the fuel cell Electrode can be made. By using the electrode in a hydrogen gas generator, the electrode can be efficiently electrolyzed, and an electrode capable of generating a sufficient amount of hydrogen gas can be produced.

  The electrode for firing the metal sheet at a temperature at which the powder of the transition metal having the lowest melting point of the at least three types of transition metals selected in the transition metal selection step is used in the porous structure alloy sheet electrode forming step is the most melting point. By joining other transition metal powders using low transition metal powder as a binder, the electrode has high strength and can maintain its shape, preventing inadvertent breakage and damage Electrode can be made. Since the electrode can maintain its shape, it is possible to use its catalytic function sufficiently and reliably, and it is preferable to use it suitably as a non-platinum anode or cathode having catalytic activity (catalytic activity). Possible electrodes can be made.

FIG. 2 is a perspective view of an electrode shown as an example. FIG. 3 is a partially enlarged front view showing an example of an electrode. FIG. 9 is a partially enlarged front view showing another example of the electrode. FIG. 3 is an exploded perspective view showing an example of a cell using electrodes. FIG. 4 is a side view of a cell using electrodes. The figure explaining the electric power generation of the fuel cell (polymer electrolyte fuel cell) using the electrode. The figure which shows the result of the electromotive force test of an electrode. The figure which shows the result of the IV characteristic test of an electrode. The figure explaining the electrolysis of the hydrogen gas generator using an electrode. FIG. 4 is a diagram illustrating a method for manufacturing the electrode 10.

  The details of the electrode according to the present invention will be described below with reference to the accompanying drawings such as FIG. 1 which is a perspective view of the electrode 10 shown as an example. FIG. 2 is a partially enlarged front view showing an example of the electrode 10, and FIG. 3 is a partially enlarged front view shown as another example of the electrode 10. In FIG. 1, the thickness direction is indicated by an arrow X, and the radial direction is indicated by an arrow Y.

  The electrode 10 is used as an anode (anode) or a cathode (cathode), and is used as an electrode (catalyst) of the fuel cell 20 (see FIG. 6) and an electrode (catalyst) of the hydrogen gas generator 29 (see FIG. 9). . The electrode 10 has a front surface 12 and a rear surface 13, has a predetermined area and a predetermined thickness L1, and is formed into a circular planar shape. The electrode 10 is an alloy thin plate electrode 15 having a porous structure having a large number of fine channels 14 (passage holes). Gas or liquid flows through the flow path 14. In addition, the planar shape of the electrode 10 is not particularly limited, and may be formed into any other planar shape in addition to the circular shape.

  The electrode 10 is formed from at least three types of transition metals selected from powdered transition metals. As the transition metal, 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.

  In the electrode 10 (alloy thin-plate electrode 15 having a porous structure), the work function of at least three kinds of selected transition metals (energy required to extract electrons from a substance) is close to the work function of a platinum group element. Thus, at least three types of transition metals are selected from the transition metals. 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).

  The electrode 10 has at least three kinds of transition metal powders selected from various transition metals (Ti (titanium) processed into a powder form, Cr (chromium) processed into a powder form, powder processed into a powder form). Mn (manganese), powdered Fe (iron), powdered Co (cobalt), powdered Ni (nickel), powdered Cu (copper), Powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver)) are uniformly mixed and dispersed. The metal powder mixture 16 is compressed into a thin plate having a predetermined area to form a thin metal plate 11, and the thin metal plate 11 is fired (see FIG. 10). The electrode 10 has a large number of fine channels 14 (passage holes) having different diameters. The electrode 10 has a large specific surface area because a large number of fine channels 14 (passage holes) are formed.

  The flow passages 14 (passage holes) have a plurality of flow openings 17 opening to the front surface 12 and a plurality of flow openings 17 opening to the rear surface 13. 10 penetrates. The flow paths 14 extend between the front surface 12 and the rear surface 13 of the electrode 10 while being bent irregularly in the thickness direction of the electrode 10, and extend from the outer peripheral edge 18 of the electrode 10 toward the center. It extends while bending in the direction irregularly. The flow paths 14 that are adjacent to each other in the radial direction and extend in the thickness direction are partially connected in the radial direction, and one flow path 14 and the other flow path 14 communicate with each other. The flow paths 14 that extend adjacent to the thickness direction and bend in the radial direction are partially connected in the thickness direction, and one flow path 14 and the other flow path 14 communicate with each other.

  The opening areas (opening diameters) of the flow passages 14 (passage holes) are not uniform in the thickness direction, are irregularly changed in the thickness direction, and are not uniform in the radial direction. , Changing irregularly in the radial direction. These flow paths 14 are irregularly opened in the thickness direction and the radial direction while the opening area (opening diameter) increases or decreases. Further, the opening area (opening diameter) of the flow opening 17 opening on the front surface 12 and the opening 17 on the rear surface 13 are not uniform, and the areas are different. The opening diameters of the flow passages 14 (passage holes) and the opening diameters of the flow openings 17 in the front and rear surfaces 12 and 13 are in the range of 1 μm to 100 μm.

  The electrode 10 (porous alloy thin plate electrode 15) has a thickness L1 in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm. If the thickness L1 of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is less than 0.03 mm, the strength is reduced, and the electrode 10 is easily broken or damaged when an impact is applied, and maintains its shape. You may not be able to. If the thickness L1 of the electrode 10 (the alloy thin plate electrode 15 having a porous structure) exceeds 0.3 mm, the electric resistance of the electrode 10 becomes large, protons cannot move smoothly through the electrode 10, and the electrode 10 When used for the battery 20, the fuel cell 20 cannot generate sufficient electricity, and cannot supply sufficient electric energy to the load 28 connected to the fuel cell 20. In addition, when the electrode 10 is used in the hydrogen gas generator 29, electrolysis cannot be performed efficiently, and the hydrogen gas generator 29 cannot generate sufficient hydrogen gas.

  Since the thickness of the electrode 10 (alloy thin plate electrode having a porous structure) is in the range of 0.03 mm to 0.3 mm, the electrode 10 has high strength and can maintain its shape. It is possible to prevent the electrode 10 from being damaged or damaged when an impact is applied. Further, the electric resistance of the electrode 10 is low, protons can move smoothly in the electrode 10, and by using the electrode 10 for the fuel cell 20, sufficient electricity can be generated in the fuel cell 20, Sufficient electric energy can be supplied to the load 28 connected to the battery 20. In addition, by using the electrode 10 in the hydrogen gas generator 29, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated in the hydrogen gas generator 29.

  The electrode 10 (the alloy thin plate electrode 15 having a porous structure) has a porosity in a range of 15% to 30%, preferably 20% to 25%, and a relative density in a range of 70% to 85%. Preferably, it is in the range of 75% to 80%. If the porosity of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is less than 15% and the relative density exceeds 85%, a large number of fine flow paths 14 (passage holes) are not formed in the electrode 10, and the electrode 10 The specific surface area of No. 10 cannot be increased. When the porosity of the electrode 10 (alloy thin plate electrode 15 having a porous structure) exceeds 30% and the relative density is less than 70%, the opening area (opening diameter) of the flow passage 14 (passage hole) and the front and rear surfaces 12 and 13 are reduced. The opening area (opening diameter) of the flow opening 17 becomes unnecessarily large, the strength of the electrode 10 is reduced, and the electrode 10 is easily damaged or damaged when an impact is applied, and the shape of the electrode 10 is maintained. It may not be possible.

  Since the porosity and the relative density of the electrode 10 (alloy thin plate electrode 15 having a porous structure) are in the above-described ranges, the electrode 10 has a large number of fine flow paths 14 (passage holes) and openings having different opening areas (opening diameters). The electrode 10 is formed into a porous shape having a number of fine front and rear surfaces 12 and 13 having different areas (opening diameters), and the specific surface area of the electrode 10 can be increased. While the gas or the liquid flows, the gas or the liquid can be brought into wide contact with the contact surface of the electrode 10 (alloy thin plate electrode 15 having a porous structure).

Electrode 10 (alloy thin plate electrode 15 of the porous structure) in the range that the density of ^{5.0g / cm 2 ~7.0g / cm 2} , preferably in ^the range of 5.5g / cm ² ~6.5g / cm 2 It is in. When the density of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is less than 5.0 g / cm ² , the strength of the electrode 10 is reduced, and the electrode 10 is easily damaged or damaged when an impact is applied, and its shape is reduced. May not be able to maintain. When the density of the electrode 10 (alloy thin plate electrode 15 having a porous structure) exceeds 7.0 g / cm ² , a large number of fine channels 14 (passage holes) are not formed in the electrode 10, and the specific surface area of the electrode 10 increases. Can not do it.

  Since the density of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is within the above range, the electrode 10 has a large number of fine flow paths 14 (passage holes) and opening areas (opening diameters) having different opening areas (opening diameters). ) Having a large number of fine front and rear surfaces 12, 13, which are formed into a porous material having a large number of flow ports 17. The specific surface area of the electrode 10 can be increased, and gas and liquid can flow through these flow paths 14 (passage holes). The gas or the liquid can be brought into wide contact with the contact surface of the electrode 10 (the alloy thin plate electrode 15 having a porous structure) while flowing.

  Ti powder (powder processed Ti), Cr powder (powder processed Cr), Mn powder (powder processed Mn), Fe powder (powder processed) Processed Fe), Co powder (Co processed into powder), Ni powder (Ni processed into powder), Cu powder (Cu processed into powder), Zn powder Powder (Zn processed into powder), Nb powder (Nb processed into powder), Mo powder (Mo processed into powder), Ag powder (processed into powder) Ag) has a particle size in the range of 10 μm to 200 μm.

  If the particle diameter of the transition metal powder is less than 10 μm, the flow path 14 (passage hole) is blocked by the transition metal, so that many fine flow paths 14 cannot be formed in the electrode 10 and the electrode 10 ( The specific surface area of the porous alloy thin plate electrode 15) cannot be increased. If the particle diameter of the transition metal powder exceeds 200 μm, the opening area (opening diameter) of the flow path 14 (passage hole) and the opening area (opening diameter) of the flow opening 17 of the front and rear surfaces 12 and 13 are more than necessary. Therefore, a large number of fine channels 14 cannot be formed in the electrode 10 (alloy thin plate electrode 15 having a porous structure), and the specific surface area of the electrode 10 cannot be increased.

  In the electrode 10 (alloy thin plate electrode 15 having a porous structure), since the particle diameter of the transition metal powder is in the above-mentioned range, the electrode 10 has a large number of fine flow paths 14 (passage holes) having different opening areas (opening diameters). ) And a large number of fine front and rear surfaces 12 and 13 having different opening areas (opening diameters), and formed into a porous material having a large number of flow ports 17, so that the specific surface area of the electrode 10 can be increased. The gas or the liquid can be brought into wide contact with the contact surface of the electrode 10 (the alloy thin plate electrode 15 having a porous structure) while the gas or the liquid flows.

  FIG. 4 is an exploded perspective view showing an example of the cell 19 using the electrode 10, and FIG. 5 is a side view of the cell 19 using the electrode 10. FIG. 6 is a diagram for explaining power generation of the fuel cell 20 (polymer electrolyte fuel cell) using the electrode 10, and FIG. 7 is a diagram showing a result of an electromotive force test of the electrode 10. FIG. 8 is a diagram showing a result of an IV characteristic test of the electrode 10.

  As an example of the cell 19 using the electrode 10, as shown in FIG. 4, a fuel electrode 21 (anode) using the electrode 10, an air electrode 22 (cathode) using the electrode 10, a fuel electrode 21 and air The solid polymer electrolyte membrane 23 (fluorine-based ion exchange membrane) interposed between the electrodes 22, the separator 24 a (bipolar plate) located outside the fuel electrode 21 in the thickness direction, and the separator 24 a located outside the thickness direction of the air electrode 22. And a separator 24b (bipolar plate). A supply channel for a reaction gas (hydrogen, oxygen, etc.) is carved (carved) in the separators 24a, 24b.

  In the cell 19, as shown in FIG. 5, the fuel electrode 21, the air electrode 22, and the solid polymer electrolyte membrane 23 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly (Membrane Electrode Assembly, MEA). The membrane / electrode assembly is sandwiched between the separators 24a and 24b. In the fuel cell 20 (polymer electrolyte fuel cell), a plurality of cells 19 (single cells) overlap in one direction and are connected in series to form a cell stack (fuel cell stack). The solid polymer electrolyte membrane 23 has proton conductivity and no electronic conductivity.

  A gas diffusion layer 25a is formed between the fuel electrode 21 and the separator 24a, and a gas diffusion layer 25b is formed between the air electrode 22 and the separator 24b. A gas seal 26a is provided between the fuel electrode 21 and the separator 24a and above and below the gas diffusion layer 25. A gas seal 26b is provided between the air electrode 22 and the separator 24b and above and below the gas diffusion layer 25b.

As shown in FIG. 6, in the fuel cell 20 (polymer electrolyte fuel cell), hydrogen (fuel) is supplied to the fuel electrode 21 (electrode 10), and air (oxygen) is supplied to the air electrode 22 (electrode 10). Is done. At the fuel electrode 21 (electrode 10), hydrogen is decomposed into protons (hydrogen ions, H ⁺ ) and electrons by a reaction (catalysis) of H ₂ → 2H ⁺ + 2e ⁻ . Thereafter, the protons move to the air electrode 22 (electrode 10) through the solid polymer electrolyte membrane 23, and the electrons move to the air electrode 22 through the conductor 27. Protons generated at the fuel electrode 21 flow through the solid polymer electrolyte membrane 23. At the air electrode 22 (electrode 10), the protons transferred from the solid polymer electrolyte membrane 23 and the electrons transferred on the conducting wire 27 react with oxygen in the air, and water is formed by the reaction of 4H ⁺ + O ₂ + 4e → 2H ₂ O. Generated. The fuel electrode 21 (electrode 10) and the air are prepared from at least three types of transition metals selected from transition metals so that the composite work function of the work functions of at least three types of transition metals approximates the work function of the platinum group element. Since the electrode 22 (electrode 10) is formed, the fuel electrode 21 and the air electrode 22 exhibit excellent catalytic activity (catalysis), and hydrogen is efficiently decomposed into protons and electrons.

  In the electromotive voltage test, a voltage (V) between the fuel electrode 21 (electrode 10) and the air electrode 22 (electrode 10) was measured for 15 minutes after hydrogen gas injection. In the diagram showing the results of the electromotive force test in FIG. 7, the horizontal axis represents the measurement time (min), and the vertical axis represents the voltage (V) between the fuel electrode 21 (electrode 10) and the air electrode 22 (electrode 10). Represents In a fuel cell using an electrode (platinum electrode) using (supporting) platinum, as shown in FIG. 7 showing the result of an electromotive force test, the voltage between the electrodes is about 1.079 (V). In contrast, in the fuel cell 20 using the electrode 10 (non-platinum electrode), the voltage (electromotive force) between the fuel electrode 21 (electrode 10) and the air electrode 22 (electrode 10) is 1.01 (electromotive force). V) to 1.02 (V).

  In the IV characteristic test, a load was connected between the fuel electrode 21 (electrode 10) and the air electrode 22 (electrode 10), and the relationship between voltage and current was measured. In FIG. 8 showing the results of the IV characteristic test, the horizontal axis represents current (A), and the vertical axis represents voltage (V). In the fuel cell using the electrode 10 (non-platinum electrode), as shown in FIG. 8 showing the result of the IV characteristic test, the voltage drop of the fuel cell using the electrode carrying platinum (platinum electrode) is shown. The result was not much different from the rate. As shown in the result of the electromotive force test in FIG. 7 and the result of the IV characteristic test in FIG. 8, the non-platinum electrode 10 that does not use a platinum group element emits electrons to generate hydrogen ions. It has been confirmed that it has a catalytic action to promote and has substantially the same oxygen reduction function (catalytic action) as an electrode using platinum.

  The electrode 10 is formed of a metal powder mixture 16 formed of at least three types of transition metals selected from various transition metals, and uniformly mixed and dispersed with at least three types of selected transition metal powders. An alloy thin plate electrode 15 having a porous structure in which a large number of fine flow paths 14 (passage holes) are formed by being compressed into a thin plate having a predetermined area and then baked to synthesize work functions of at least three selected transition metals. Since at least three types of transition metals are selected from various transition metals so that the work function approximates the work function of the platinum group element, the transition metal has substantially the same work function as the platinum group element. It can exhibit substantially the same catalytic activity (catalysis) as that of the fuel cell 20, and can be suitably used as the fuel electrode 21 (anode) and the air electrode 22 (cathode) of the fuel cell 20.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) is formed of at least three types of transition metals selected from various transition metals, does not use an expensive platinum group element, and is a non-platinum fuel electrode. 21 (anode) and air electrode 22 (cathode) can be manufactured at low cost. Since the thickness of the electrode 10 (alloy thin plate electrode 15 having a porous structure) is in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode 10 is low, and protons can move smoothly through the electrode 10. By using the electrode 10 for the fuel cell 20, sufficient electricity can be generated in the fuel cell 20, and sufficient electric energy can be supplied to the load 28 connected to the fuel cell 20.

FIG. 9 is a diagram illustrating electrolysis of the hydrogen gas generator 29 using the electrode 10. As an example of the hydrogen gas generator 29 using the electrode 10, as shown in FIG. 9, an anode 31 (anode) using the electrode 10, a cathode 30 (cathode) using the electrode 10, an anode 31 and a cathode 30 , a solid polymer electrolyte membrane 32 (fluorine-based ion exchange membrane), an anode power supply member 33b and a cathode power supply member 33a , an anode water reservoir 34b and a cathode water reservoir 34a, and an anode main electrode 35b. And a cathode main electrode 35a .

In the hydrogen gas generator 29, the anode 31 , the cathode 30 , and the solid polymer electrolyte membrane 32 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly (Membrane Electrode Assembly, MEA). The anode power supply member 33b and the cathode power supply member 33a are sandwiched. The solid polymer electrolyte membrane 32 has proton conductivity and no electronic conductivity. The anode power supply member 33b is located outside of the anode 31 in close contact with the anode 31, to feed the + current to the anode 31. Anode reservoir 34b is located outside of the anode power supply member 33b is in close contact with the anode power supply member 33b. The anode main electrode 35b is located outside the anode water storage tank 34b and supplies a positive current to the anode power supply member 33b . Cathode power supply member 33a is in close contact with the cathode 30 is located outside of the cathode 30, the cathode 30 - feeding the current. Cathode reservoir 34a is in close contact with the cathode power supply member 33a is located outside of the cathode power supply member 33a. The cathode main electrode 35a is located outside the cathode water storage tank 34a and supplies a negative current to the cathode power supply member 33a .

In the hydrogen gas generator 20, as shown by arrows in FIG. 9, water (H ₂ O) is supplied to the anode water storage tank 34b and the cathode water storage tank 34a , and a positive current is supplied from the power supply to the anode main electrode 35b. At the same time, a negative current is supplied from the power supply to the cathode main electrode 35a . The + current supplied to the anode main electrode 35b is supplied from the anode power supply member 33b to the anode 31 (anode), and the-current supplied to the cathode main electrode 35a is supplied from the cathode power supply member 33a to the cathode 30 (cathode). Is done. At the anode 31 (electrode 10), oxygen is generated by the anodic reaction (catalysis) of 2H ₂ O → 4H ⁺ + 4e ⁻ + O ₂ , and at the cathode 30 (electrode 10), the cathode reaction of 4H ⁺ + 4e ⁻ → 2H ₂ ( Oxygen is generated by the catalytic action. Protons (hydrogen ions: H ⁺ ) move through the solid polymer electrolyte membrane 32 to the cathode 30 (electrode 10). Protons generated at the anode 31 flow through the solid polymer electrolyte membrane 32. The anode 31 (electrode 10) and the cathode 30 are formed from at least three types of transition metals selected from transition metals so that the composite work function of the work functions of at least three types of transition metals approximates the work function of the platinum group element. Since the (electrode 10) is formed, the anode 31 and the cathode 30 exhibit excellent catalytic activity (catalytic action).

  As an example of the electrode 10 formed from a transition metal, a powdered Ni (nickel) powder is used as a main component, and the Ni powder and other transition metal processed into a powdered form other than Ni ( Powdery Ti (titanium), powdery Cr (chromium), powdery Mn (manganese), powdery Fe (iron), powdery Co (cobalt), powdery Cu (copper), powdery Metal powder obtained by uniformly mixing and dispersing powders of Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), and powdered Ag (silver). The mixture 16 is compressed into a thin plate having a predetermined area, and the metal powder mixture 16 is fired to form a porous metal sheet 15 having a large number of fine channels 14 (pass holes).

  The electrode 10 mainly composed of Ni (nickel) powder (alloy thin plate electrode 15 having a porous structure) is formed into a porous thin plate having a large number of fine channels 14 (passage holes), and has a thickness dimension. Is in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm. The electrode 10 mainly composed of Ni powder (the alloy thin plate electrode 15 having a porous structure) has a composite work function of the work function of Ni and the work function of at least two types of transition metals other than Ni, which is a platinum group element. Are selected from at least two types of transition metals other than the Ni powder from various transition metals so as to approximate the work function of the transition metal. In the electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Ni powder, the transition metal powder having the lowest melting point is melted during firing of the metal powder mixture 16 compressed into a thin plate having a predetermined area. The powder of another transition metal is joined using the molten transition metal as a binder.

  In the electrode 10 mainly composed of Ni (nickel) powder (alloy thin plate electrode 15 having a porous structure), the weight ratio of the powdered Ni metal powder mixture 16 to the total weight of the metal powder mixture 16 is 30% to 50%. , At least one kind of transition metal (powder Ti (titanium), powdery Cr (chromium), powdery Mn (manganese), powdery Fe (iron) excluding Ni Of powdery Co (cobalt), powdery Cu (copper), powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver) At least one type of metal powder mixture 16 is in the range of 20% to 50% with respect to the total weight, and at least one other type of transition metal (powder Ti (Titanium), powdered Cr (chromium), powdered Mn (manganese), powdered Fe (iron), powdered Co (cobalt), powdered Cu (copper), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag ( The weight ratio of the metal powder mixture 16 of at least one of (silver) to the total weight is in the range of 3% to 20%. The weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture 16 is in the range of 3% to 20%.

  Specific examples of the electrode 10 containing Ni (nickel) powder as a main component include metal powder obtained by uniformly mixing and dispersing Ni powder, Cu (copper) powder, and ZN (zinc) powder. The alloy thin plate electrode 15 having a porous structure in which a plurality of fine channels 14 (passage holes) are formed by compressing the mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a weight ratio of the Ni powder of 48% to the total weight of the metal powder mixture 16, a Cu powder weight ratio of 42% to the total weight of the metal powder mixture 16, The powder weight ratio of Zn to the total weight 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 Zn powder is melted, and the molten Zn serves as a binder to form Ni powder and Cu. And powder.

  Other specific examples of the electrode 10 mainly composed of Ni (nickel) powder include a metal in which Ni powder, Mn (manganese) powder, and Mo (molybdenum) powder are uniformly mixed and dispersed. An alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing a powder mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a weight ratio of the Ni powder of 48% to the total weight of the metal powder mixture 16, a powder weight ratio of Mn to the total weight of the metal powder mixture 16 of 7%, The powder weight ratio of Mo to the total weight 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 powder is melted, and the molten Mn serves as a binder to form Ni powder and Mo powder. Are joined.

The electrode 10 (alloy thin plate electrode 15 having a porous structure) formed of a powder of Ni (nickel) as a main component and having a thickness in the range of 0.03 mm to 0.3 mm has a work function of Ni and other than Ni. At least two types of transition metal powder excluding Ni powder from various transition metals so that the composite work function of at least two types of transition metals and the work function of the transition metal approximates the work function of the platinum group element. Since the body is selected, it has substantially the same work function as the platinum group element, and can exhibit substantially the same catalytic activity (catalytic action) as the platinum group element, such as the fuel cell 20 and the hydrogen gas generator 29. Can be suitably used as the fuel electrode 20, the anode 31 (anode) or the air electrode 21, and the cathode 30 (cathode).

The electrode 10 (alloy thin plate electrode 15 having a porous structure) is formed of Ni powder and at least two types of transition metal powder other than Ni powder selected from various transition metals, Since an expensive platinum group element is not used, the non-platinum fuel electrode 20, anode 31 , air electrode 21, and cathode 30 can be manufactured at low cost. Since the thickness of the electrode 10 containing Ni as a main component (the alloy thin plate electrode 15 having a porous structure) is in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode 10 is low, and protons are smoothly applied to the electrode 10. By using the electrode 10 for the fuel cell 20, sufficient electric power can be generated in the fuel cell 20 and sufficient electric energy can be supplied to the load connected to the fuel cell 20. By using the electrode 10 in the hydrogen gas generator 29, the electrolysis can be efficiently performed, and the hydrogen gas generator 29 can generate a sufficient amount of hydrogen gas.

  As another example of the electrode 10 formed from a transition metal, other transitions processed into a powdered form excluding Fe powder and Fe mainly containing powdered Fe (iron) powder. Metal (powder Ti (titanium), powdery Cr (chromium), powdery Mn (manganese), powdery Co (cobalt), powdery Ni (nickel), powdery Cu (copper), A metal obtained by uniformly mixing and dispersing powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver) powders. An alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing a powder mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Fe (iron) powder is formed into a porous thin plate having a large number of fine channels 14 (passage holes), and has a thickness dimension. Is in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm. The electrode 10 mainly composed of Fe powder (the alloy thin plate electrode 15 having a porous structure) has a composite work function of the work function of Fe and the work function of at least two types of transition metals other than Fe, which is a platinum group element. Are selected from among various transition metals, at least two types of transition metal powders excluding the Fe powder. In the electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Fe powder, the transition metal powder having the lowest melting point is melted during firing of the metal powder mixture 16 compressed into a thin plate having a predetermined area. The powder of another transition metal is joined using the molten transition metal as a binder.

  In the electrode 10 containing Fe (iron) powder as a main component, the weight ratio of the powdered Fe metal powder mixture 16 to the total weight is in the range of 30% to 50%. Processed at least one transition metal (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Co (cobalt), powder Ni (nickel), Metal powder of powdered Cu (copper), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver)) The weight ratio to the total weight of the mixture 16 is in the range of 20% to 50%, and at least one other transition metal (powder Ti (titanium), powder Cr ( Chromium), powdered Mn (manganese), powdered Co (cobalt), powdered Ni (nickel) At least one of powdered Cu (copper), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), and powdered Ag (silver) )) Is in the range of 3% to 20% with respect to the total weight of the metal powder mixture 16. The weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture 16 is in the range of 3% to 20%.

  Specific examples of the electrode 10 containing Fe (iron) powder as a main component include metal powder obtained by uniformly mixing and dispersing Fe powder, Ni (nickel) powder, and Cu (copper) powder. The alloy thin plate electrode 15 having a porous structure in which a plurality of fine channels 14 (passage holes) are formed by compressing the mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a weight ratio of the Fe powder of 48% with respect to the total weight of the metal powder mixture 16, a weight ratio of the Ni powder of 48% with respect to the total weight of the metal powder mixture 16, and the metal powder mixture 16. The weight ratio of Cu powder to the total weight of 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 Cu powder is melted, and the molten Cu serves as a binder to form the Fe powder and the Ni powder. Has joined the body.

  Other specific examples of the electrode 10 containing Fe (iron) powder as a main component include a metal obtained by uniformly mixing and dispersing Fe powder, Ti (titanium) powder, and Ag (silver) powder. An alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing a powder mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a Fe powder weight ratio of 48% with respect to the total weight of the metal powder mixture 16, a Ti powder weight ratio of 46% with respect to the total weight of the metal powder mixture 16, and a metal powder mixture 16. The powder weight ratio of Ag to the total weight 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 powder is melted, and the molten Ag serves as a binder to form the Fe powder and the Ti powder. Has joined the body.

The electrode 10 (alloy thin plate electrode 15 having a porous structure) formed of a powder of Fe as a main component and having a thickness in the range of 0.03 mm to 0.3 mm has a work function of Fe and at least two types other than Fe. At least two transition metal powders other than Fe powder are selected from various transition metals so that the work function of the transition metal and the work function of the transition metal are close to the work function of the platinum group element. Therefore, it has substantially the same work function as the platinum group element, can exhibit substantially the same catalytic activity (catalysis) as the platinum group element, and has a fuel electrode such as the fuel cell 20 and the hydrogen gas generator 29. 20, the anode 31 (anode) or the air electrode 21, and the cathode 30 (cathode) can be suitably used.

The electrode 10 (alloy thin-plate electrode 15 having a porous structure) is formed from a powder of Fe and a powder of at least two types of transition metals other than a powder of Fe selected from various transition metals, Since an expensive platinum group element is not used, the non-platinum fuel electrode 20, anode 31 , air electrode 21, and cathode 30 can be manufactured at low cost. Since the electrode 10 containing Fe as a main component (alloy thin plate electrode 15 having a porous structure) has a thickness in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode 10 is low, and protons are smoothly applied to the electrode 10. By using the electrode 10 for the fuel cell 20, sufficient electric power can be generated in the fuel cell 20 and sufficient electric energy can be supplied to the load connected to the fuel cell 20. By using the electrode 10 for the hydrogen gas generator 29, the electrolysis can be performed efficiently, and the hydrogen gas generator 29 can generate a sufficient hydrogen gas.

  As another example of the electrode 10 formed from a transition metal, other transitions processed into a powdered state excluding Cu powder and Cu as a main component are powdered Cu (copper) powder. Metal (powder Ti (titanium), powdery Cr (chromium), powdery Mn (manganese), powdery Fe (iron), powdery Co (cobalt), powdery Ni (nickel), A metal obtained by uniformly mixing and dispersing powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver) powders. An alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing a powder mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16.

  The electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Cu (copper) powder is formed into a porous thin plate having a large number of fine channels 14 (passage holes), and has a thickness dimension. Is in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm. The electrode 10 mainly composed of Cu powder (the alloy thin plate electrode 15 having a porous structure) has a composite work function of the work function of Cu and the work function of at least two types of transition metals other than Cu, which is a platinum group element. , At least two types of transition metal powder other than the Cu powder are selected from various transition metals. In the electrode 10 (alloy thin plate electrode 15 having a porous structure) mainly composed of Cu powder, the transition metal powder having the lowest melting point is melted during firing of the metal powder mixture 16 compressed into a thin plate having a predetermined area. The powder of another transition metal is joined using the molten transition metal as a binder.

  In the electrode 10 mainly composed of Cu (copper) powder, the weight ratio of the Cu metal powder mixture 16 processed into a powder to the total weight is in the range of 30% to 50%, Processed at least one transition metal (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Fe (iron), powder Co (cobalt), Metal powder of powdered Ni (nickel), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver)) The weight ratio to the total weight of the mixture 16 is in the range of 20% to 50%, and at least one other transition metal (powder Ti (titanium), powder Cr ( Chromium), powdered Mn (manganese), powdered Fe (iron), powdered Co (cobalt) Powdered Ni (nickel), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (silver), and at least one other metal) The weight ratio of the powder mixture 16 to the total weight is in the range of 3% to 20%. The weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture 16 is in the range of 3% to 20%.

  Specific examples of the electrode 10 mainly composed of Cu (copper) powder include metal powder obtained by uniformly mixing and dispersing Cu powder, Fe (iron) powder, and Zn (zinc) powder. The alloy thin plate electrode 15 having a porous structure in which a plurality of fine channels 14 (passage holes) are formed by compressing the mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a Cu powder weight ratio of 48% with respect to the total weight of the metal powder mixture 16, a Fe powder weight ratio of 48% with respect to the total weight of the metal powder mixture 16, The powder weight ratio of Zn to the total weight is 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 Zn powder is melted, and the molten Zn serves as a binder to form the Cu powder and Fe. And powder.

  Specific examples of the electrode 10 mainly containing Cu (copper) powder include metal powder obtained by uniformly mixing and dispersing Cu powder, Fe (iron) powder, and Ag (silver) powder. The alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) are formed by compressing the mixture 16 into a thin plate having a predetermined area and baking the metal powder mixture 16. The electrode 10 has a Cu powder weight ratio of 48% with respect to the total weight of the metal powder mixture 16, a Fe powder weight ratio of 46% with respect to the total weight of the metal powder mixture 16, and a metal powder mixture 8 of The powder weight ratio of Ag to the total weight 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 powder is melted, and the molten Ag serves as a binder to form the Cu powder and Fe. And powder.

The electrode 10 (alloy thin plate electrode 15 having a porous structure) formed of a Cu powder as a main component and having a thickness in the range of 0.03 mm to 0.3 mm has a work function of Cu and at least two types other than Cu. At least two other transition metal powders except for the Cu powder are selected from various transition metals so that the work function of the transition metal and the work function of the transition metal are close to the work function of the platinum group element. Therefore, it has substantially the same work function as the platinum group element, can exhibit substantially the same catalytic activity (catalysis) as the platinum group element, and has a fuel electrode such as the fuel cell 20 and the hydrogen gas generator 29. 20, the anode 31 (anode) or the air electrode 21, and the cathode 30 (cathode) can be suitably used.

The electrode 10 (alloy thin plate electrode 15 having a porous structure) is formed from a powder of Cu and a powder of at least two types of transition metals other than a powder of Cu selected from various transition metals, Since an expensive platinum group element is not used, the non-platinum fuel electrode 20, anode 31 , air electrode 21, and cathode 30 can be manufactured at low cost. Since the electrode 10 mainly composed of Cu (alloy thin plate electrode 15 having a porous structure) has a thickness in the range of 0.03 mm to 0.3 mm, the electric resistance of the electrode is low, and protons move smoothly through the electrode. By using the electrode 10 for the fuel cell 20, sufficient electricity can be generated in the fuel cell 20 and sufficient electric energy can be supplied to the load connected to the fuel cell 20. At the same time, by using the electrode 10 for the hydrogen gas generator 29, electrolysis can be performed efficiently, and sufficient hydrogen gas can be generated in the hydrogen gas generator 29.

  FIG. 10 is a diagram illustrating a method for manufacturing the electrode 10. As shown in FIG. 10, the electrode 10 is manufactured by an electrode manufacturing method including a transition metal selection step S1, a metal powder mixture creation step S2, a metal sheet creation step S3, and a porous structure alloy sheet electrode creation step S4. In the transition metal selection step S1, the various transition metals 36 are selected from various transition metals 36 such that the composite work function of the work functions of at least three types of transition metals 36 selected from the various transition metals 36 is close to the work function of the platinum group element. At least three types of transition metals 36 (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 electrode 10 mainly containing Ni (nickel), Cu (copper) and ZN (zinc) are selected, or Mn (manganese) and Mo (molybdenum) are used. Select For the electrode 10 mainly containing Fe (iron), Ni (nickel) and Cu (copper) are selected, or Ti (titanium) and Ag (silver) are selected. For the electrode 10 mainly containing Cu (copper), Fe (iron) and Zn (zinc) are selected, or Fe (iron) and Ag (silver) are selected.

  In the metal powder mixture preparation step S2, a metal powder mixture 16 is prepared by uniformly mixing and dispersing powders of at least three types of transition metals 36 selected in the transition metal selection step S1. In the metal powder mixture forming step S2, in the electrode 10 containing Ni (nickel) as a main component, each of Ni, Cu (copper) and ZN (zinc) selected in the transition metal selecting step S1 is 10 μm by a pulverizer. Finely pulverized to a particle size of ~ 200 µm to produce Ni powder, Cu powder and Zn powder. Next, Ni powder, Cu powder, and Zn powder are put into a mixer, and the Ni powder, Cu powder, and Zn powder are stirred and mixed by the mixer, and the Ni powder is mixed. A metal powder mixture 16 in which the powder, Cu powder and Zn powder are uniformly mixed and dispersed is produced. Alternatively, each of Ni (nickel), Mn (manganese), and Mo (molybdenum) 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 to obtain a Ni powder, Mn powder. Powder and Mo powder are prepared. Next, Ni powder, Mn powder, and Mo powder are put into a mixer, and the Ni powder, Mn powder, and Mo powder are stirred and mixed by the mixer, and the Ni powder is mixed. A metal powder mixture 16 in which powder, Mn powder, and Mo powder are uniformly mixed and dispersed is produced.

  In the metal powder mixture preparation step S2, in the electrode 10 containing Fe (iron) as a main component, each of Fe, Ni (nickel), and Cu (copper) selected in the transition metal selection step S1 was reduced to 10 μm by a pulverizer. Finely pulverized to a particle size of ~ 200 µm to produce Fe powder, Ni powder and Cu powder. Next, the Fe powder, the Ni powder, and the Cu powder are put into a mixer, and the Fe powder, the Ni powder, and the Cu powder are stirred and mixed by the mixer, and the Fe powder is mixed. A metal powder mixture 16 is prepared in which the powder, Ni powder and Cu powder 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 to obtain a powder of Fe, Powder and Ag powder are prepared. Next, the Fe powder, the Ti powder, and the Ag powder are put into a mixer, and the Fe powder, the Ti powder, and the Ag powder are stirred and mixed by the mixer, and the Fe powder is mixed. A metal powder mixture 16 in which the powder, Ti powder and Ag powder are uniformly mixed and dispersed is produced.

  In the metal powder mixture preparation step S2, in the electrode 10 containing Cu (copper) as a main component, each of Cu, Fe (iron) and Zn (zinc) selected in the transition metal selection step S1 is reduced to 10 μm by a pulverizer. Finely pulverized to a particle size of ~ 200 µm to produce Cu powder, Fe powder and Zn powder. Next, Cu powder, Fe powder, and Zn powder are put into a mixer, and the Cu powder, Fe powder, and Zn powder are stirred and mixed by the mixer, and the Cu powder is mixed. A metal powder mixture 16 in which powder, Fe powder, and Zn powder 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 size of 10 μm to 200 μm by a fine pulverizer, and Cu powder, Fe powder Powder and Ag powder are prepared. Next, the Cu powder, the Fe powder, and the Ag powder are put into a mixer, and the Cu powder, the Fe powder, and the Ag powder are stirred and mixed by the mixer, and the Cu powder is mixed. A metal powder mixture 16 in which powder, Fe powder and Ag powder are uniformly mixed and dispersed is produced.

  In the metal sheet forming step S3, the metal powder mixture 16 formed in the metal powder mixture forming step S2 is pressurized at a predetermined pressure, and the metal powder mixture 16 is compressed into a sheet having a predetermined area to form a metal sheet 11. In the metal sheet making step S3, the metal powder mixture 16 is put into a mold, and the metal sheet 11 is made by press working in which the mold is pressed (pressed) by a press machine. The press pressure (pressure) at the time of press working is in the range of 500 MPa to 800 MPa. When the pressing pressure (pressure) is less than 500 MPa, the opening area (opening diameter) of the flow path 14 (passage hole) formed in the metal thin plate 11 increases, and the thickness of the metal thin plate 11 is reduced to 0.03 mm to 0.3 mm. On the other hand, a large number of fine channels 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm cannot be formed in the metal sheet 11. If the pressing pressure (pressure) exceeds 800 MPa, the opening area (opening diameter) of the flow path 14 (passage hole) formed in the metal thin plate 11 becomes unnecessarily small, and the thickness of the metal thin plate 11 becomes 0.03 mm or more. A large number of fine flow paths 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm cannot be formed in the metal thin plate 11 while the diameter is set to 0.3 mm. In the electrode manufacturing method, the metal powder mixture 16 is pressurized (compressed) at a pressure in the above range, so that the thickness of the metal thin plate 11 is 0.03 mm to 0.3 mm and the opening diameter is in the range of 1 μm to 100 μm. The metal sheet 11 having a large number of fine channels 14 (passage holes) can be formed.

  In the metal thin plate forming step S3, in the electrode 10 containing Ni (nickel) as a main component, a predetermined amount of a metal powder mixture 16 obtained by mixing Ni powder, Cu (copper) powder, and ZN (zinc) powder. Is put into a mold, the metal powder mixture 16 is pressed (compressed) by press working to compress the metal powder mixture 16 into a thin plate having a predetermined area, and has a thickness of 0.03 mm to 0.3 mm. Then, a metal sheet 11 having a large number of fine channels 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm is produced. Alternatively, a predetermined amount of a metal powder mixture 16 obtained by mixing Ni powder, Mn (manganese) powder, and Mo (molybdenum) powder is charged into a mold, and the metal powder mixture 16 is pressed. The metal powder mixture 16 is compressed into a thin plate having a predetermined area by pressurization (compression), and a large number of fine channels having a thickness of 0.03 mm to 0.3 mm and an opening diameter of 1 μm to 100 μm. The metal sheet 11 having the holes 14 (passage holes) is formed.

  In the metal thin plate forming step S3, the electrode 10 containing Fe (iron) as a main component has a metal powder mixture 16 obtained by mixing Fe powder, Ni (nickel) powder, and Cu (copper) powder. The fixed amount is put into a mold, and the metal powder mixture 16 is pressed (compressed) by pressing to compress the metal powder mixture 16 into a thin plate having a predetermined area, and the thickness dimension is 0.03 mm to 0.3 mm. Then, the metal sheet 11 having a large number of fine channels 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm is formed. Alternatively, a predetermined amount of a metal powder mixture 16 obtained by mixing Fe powder, Ti (titanium) powder, and Ag (silver) powder is charged into a mold, and the metal powder mixture 16 is pressed. The metal powder mixture 16 is compressed into a thin plate having a predetermined area by pressurization (compression), and a large number of fine channels having a thickness of 0.03 mm to 0.3 mm and an opening diameter of 1 μm to 100 μm. The metal sheet 11 having the holes 14 (passage holes) is formed.

  In the metal thin plate forming step S3, the electrode 10 containing Cu (copper) as a main component has a metal powder mixture 16 obtained by mixing Cu powder, Fe (iron) powder, and Zn (zinc) powder. The fixed amount is put into a mold, and the metal powder mixture 16 is pressed (compressed) by pressing to compress the metal powder mixture 16 into a thin plate having a predetermined area, and the thickness dimension is 0.03 mm to 0.3 mm. Then, the metal sheet 11 having a large number of fine channels 14 (passage holes) having an opening diameter in the range of 1 μm to 100 μm is formed. Alternatively, a predetermined amount of a metal powder mixture 16 in which Cu powder, Fe (iron) powder, and Ag (silver) powder are mixed is put into a mold, and the metal powder mixture 16 is pressed. The metal powder mixture 16 is compressed into a thin plate having a predetermined area by pressurization (compression), and a large number of fine channels having a thickness of 0.03 mm to 0.3 mm and an opening diameter of 1 μm to 100 μm. The metal sheet 11 having the holes 14 (passage holes) is formed.

  In the porous structure alloy thin plate electrode forming step S4, the metal thin plate 11 formed in the metal thin plate forming step S3 is put into a furnace (electric furnace), and the metal thin plate 11 is fired (sintered) at a predetermined temperature in the furnace to obtain a large number of pieces. An alloy thin plate electrode 15 (electrode 10) having a porous structure in which fine channels 14 (passage holes) are formed is produced. In the porous structure alloy sheet electrode forming step S4, the metal sheet 11 is held for a long time at a temperature at which the powder of the transition metal 36 having the lowest melting point among the at least three types of transition metals 36 selected in the transition metal selection step S3 is melted. Bake. The firing (sintering) time is 3 hours to 6 hours. In the porous structure alloy thin plate electrode forming step S4, the powder of the transition metal 36 having the lowest melting point is melted during firing of the thin metal plate 11 (metal powder mixture 16) compressed into a thin plate having a predetermined area, and the melted transition metal is melted. Using the metal 36 as a binder, the powder of another transition metal 36 is joined (fixed).

  In the porous alloy thin plate electrode forming step S4, in the electrode 10 containing Ni (nickel) as a main component, a metal powder mixture 16 obtained by mixing Ni powder, Cu (copper) powder, and ZN (zinc) powder is used. Is compressed in a furnace (electric furnace) for a long time to form an alloy thin plate electrode 15 (electrode having a porous structure) in which a large number of fine channels 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. Make 10). In the metal sheet 11 formed of Ni powder, Cu powder, and Zn powder, the metal sheet 11 was fired and melted at a temperature (for example, 500 ° C. to 800 ° C.) at which the Zn powder was melted. The Ni powder and the Cu powder are joined (fixed) by the Zn powder.

  In the electrode 10 containing Ni (nickel) as a main component, the metal thin plate 11 obtained by compressing a metal powder mixture 16 obtained by mixing Ni powder, Mn (manganese) powder, and Mo (molybdenum) powder is used. Baking is performed in a furnace (electric furnace) for a long time to form an alloy thin plate electrode 15 (electrode 10) having a porous structure in which a large number of fine flow paths 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. In the metal sheet 11 formed from Ni powder, Mn powder, and Mo powder, the metal sheet 11 was fired and melted at a temperature at which the Mn powder was melted (for example, 1200 ° C. to 1400 ° C.). The Mn powder and the Mo powder are joined (fixed) by the Mn powder.

  In the porous structure alloy thin plate electrode forming step S4, in the electrode 10 containing Fe (iron) as a main component, a metal powder mixture obtained by mixing Fe powder, Ni (nickel) powder, and Cu (copper) powder 16 is sintered in a furnace (electric furnace) for a long time, and an alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm is formed. An electrode 10) is made. In the metal sheet 11 formed from the powder of Fe, the powder of Ni, and the powder of Cu, the metal sheet 11 was baked at a temperature at which the powder of Cu was melted (for example, 1100 ° C. to 1300 ° C.) and melted. The Fe powder and the Ni powder are joined (fixed) by the Cu powder.

  Further, in the electrode 10 containing Fe (iron) as a main component, the metal thin plate 11 obtained by compressing a metal powder mixture 16 obtained by mixing Fe powder, Ti (titanium) powder, and Ag (silver) powder is used. Baking is performed in a furnace (electric furnace) for a long time to form an alloy thin plate electrode 15 (electrode 10) having a porous structure in which a large number of fine flow paths 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. In the metal sheet 11 formed from the powder of Fe, the powder of Ti, and the powder of Ag, the metal sheet 11 is baked and melted at a temperature at which the Ag powder is melted (for example, 1000 ° C. to 1200 ° C.). The Ag powder joins (fixes) the Fe powder and the Ti powder.

  In the porous structure alloy thin plate electrode forming step S4, in the electrode 10 containing Cu (copper) as a main component, a metal powder mixture obtained by mixing Cu powder, Fe (iron) powder, and Zn (zinc) powder. 16 is sintered in a furnace (electric furnace) for a long time, and an alloy thin plate electrode 15 having a porous structure in which a number of fine channels 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm is formed. An electrode 10) is made. In the metal sheet 11 formed of Cu powder, Fe powder, and Zn powder, the metal sheet 11 was fired and melted at a temperature at which the Zn powder was melted (for example, 500 ° C. to 800 ° C.). The Cu powder and the Fe powder are joined (fixed) by the Zn powder.

  In the electrode 10 containing Cu (copper) as a main component, the metal thin plate 11 obtained by compressing a metal powder mixture 16 obtained by mixing Cu powder, Fe (iron) powder, and Ag (silver) powder is used. Baking is performed in a furnace (electric furnace) for a long time to form an alloy thin plate electrode 15 (electrode 10) having a porous structure in which a large number of fine flow paths 14 (passage holes) having an opening diameter in a range of 1 μm to 100 μm are formed. In the metal sheet 11 formed of Cu powder, Fe powder, and Ag powder, the metal sheet 11 was fired and melted at a temperature at which the Ag powder was melted (for example, 1000 ° C. to 1100 ° C.). The Cu powder and the Fe powder are bonded (fixed) by the Ag powder.

The electrode manufacturing method is such that the thickness dimension L1 is in the range of 0.03 mm to 0.3 mm by the transition metal selection step S1, the metal powder mixture creation step S2, the metal sheet creation step S3, and the porous structure alloy sheet electrode creation step S4. The electrode 10 having a large number of fine channels 14 (passage holes) can be formed, and the non-platinum fuel electrode 20, the anode 31 , the air electrode 21, and the cathode 30 that do not use a platinum group element can be manufactured at low cost. Non-platinum, which can utilize the catalytic function sufficiently and reliably and has catalytic activity (catalytic activity) and can be used as the fuel electrode 20, the anode 31 , the air electrode 21, and the cathode 30 Electrode 10 can be made.

  According to the electrode manufacturing method, the electrode 10 having a thickness in the range of 0.03 mm to 0.3 mm and having many fine channels 14 (passage holes) can be formed. And the protons can move smoothly through the electrode 10, generating sufficient electricity in the fuel cell 20 and supplying sufficient electric energy to the load 28 connected to the fuel cell 20. An electrode 10 that can be supplied can be made. According to the electrode manufacturing method, the electrolysis can be efficiently performed in the hydrogen gas generator 29, and the electrode 10 capable of generating sufficient hydrogen gas in the hydrogen gas generator 29 can be manufactured.

DESCRIPTION OF SYMBOLS 10 Electrode 11 Metal thin plate 12 Front surface 13 Rear surface 14 Channel (passage hole)
Reference Signs List 15 Alloy thin plate electrode having porous structure 16 Metal powder mixture 17 Flow opening 18 Outer rim 19 Cell 20 Fuel cell 21 Fuel electrode 22 Air electrode 23 Solid polymer electrolyte membrane 24a, b Separator (bipolar plate)
25a, b Gas diffusion layer 26a, b Gas seal 27 Conductor 28 Load 29 Hydrogen gas generator 30 Cathode 31 Anode 32 Solid polymer electrolyte membrane 33a Cathode power supply member 33b Anode power supply member 34a Cathode reservoir 34b Cathode reservoir 35a Cathode Main electrode 35b Anode main electrode 36 Transition metal

Claims (16)

In an electrode used as an anode or a cathode,
The electrode is formed of at least three types of transition metals selected from various types of transition metals, and a metal powder mixture obtained by uniformly mixing and dispersing at least three types of selected transition metal powders in a predetermined area. A porous alloy thin plate electrode having a large number of fine channels formed by firing after being compressed into a thin plate, wherein the thickness of the porous thin plate electrode is in the range of 0.03 mm to 0.3 mm. In the alloy thin plate electrode having the porous structure, 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. Wherein the transition metal is selected.   The porous alloy thin plate electrode is formed of a Ni powder as a main component and has a thickness in the range of 0.03 mm to 0.3 mm. In the porous alloy thin plate electrode, the work function of Ni and the Ni And at least two other transition metals excluding Ni powder from the 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-mentioned ones is close to the work function of the platinum group element. 2. The electrode according to claim 1, wherein a type of transition metal powder is selected.   The weight ratio of the Ni powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the total weight of the one type of transition metal powder excluding the Ni powder is the total of the metal powder mixture. The weight ratio to the weight is in a range of 20% to 50%, and the weight ratio of at least one transition metal powder other than the Ni powder to the total weight of the metal powder mixture is 3%. 3. The electrode according to claim 2, which is in the range of ~ 20%.   The porous alloy thin plate electrode is formed into a thickness of 0.03 mm to 0.3 mm with Fe powder as a main component, and the work function of the Fe and the Fe And at least two other transition metals excluding Fe powder from the various transition metals so that the work function of the transition metal and the work function of at least two types of transition metals other than that of the transition metal approximates the work function of the platinum group element. 2. The electrode according to claim 1, wherein a type of transition metal powder is selected.   The weight ratio of the Fe powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the total of the metal powder mixture of one type of transition metal powder excluding the Fe powder is The weight ratio to the weight is in the range of 20% to 50%, and the weight ratio of at least one transition metal powder other than the Fe powder to the total weight of the metal powder mixture is 3%. 5. The electrode according to claim 4, which is in the range of ~ 20%.   The porous alloy thin plate electrode is formed to have a thickness in the range of 0.03 mm to 0.3 mm with a Cu powder as a main component, and the work function of the Cu and the Cu At least two other transition metals excluding Cu powder from the various transition metals such that the work function of the transition metal and the work function of at least two other transition metals other than that of the transition metal approximates the work function of the platinum group element. 2. The electrode according to claim 1, wherein a type of transition metal powder is selected.   The weight ratio of the Cu powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the total of the metal powder mixture of one type of transition metal powder excluding the Cu powder The weight ratio to the weight is in the range of 20% to 50%, and the weight ratio of at least one transition metal powder other than the Cu powder to the total weight of the metal powder mixture is 3%. 7. The electrode according to claim 6, which is in the range of ~ 20%.   The electrode according to any one of claims 1 to 7, wherein the porosity of the alloy thin plate electrode having a porous structure is in a range of 15% to 30%. The density of the alloy thin electrodes of porous ^structure, the electrode according to any claims 1 to 8 is in the range of ^{5.0g / cm 2 ~7.0g / cm 2} .   The electrode according to any one of claims 1 to 9, wherein a particle size of the transition metal powder is in a range of 10 µm to 200 µm.   In the alloy thin plate electrode having the porous structure, the powder of the transition metal having the lowest melting point is melted during firing of the metal powder mixture compressed into a thin plate having a predetermined area, and the molten transition metal is used as a binder to form another transition metal. The electrode according to any one of claims 1 to 10, wherein a powder is bonded.   The electrode according to claim 11, wherein the weight ratio of the transition metal powder serving as the binder to the total weight of the metal powder mixture is in a range of 3% to 20%.   The electrode has at least three types of transition metals among the various 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 is close to a work function of a platinum group element. A transition metal selection step of selecting a metal, a metal powder mixture creation step of uniformly mixing and dispersing at least three types of transition metal powders selected by the transition metal selection step, Pressing the metal powder mixture produced by the metal powder mixture producing step at a predetermined pressure to produce a metal sheet; and firing the metal sheet produced by the metal sheet producing step at a predetermined temperature to produce a large number of sheets. And a porous alloy thin plate electrode forming step of forming the porous alloy thin plate electrode having the fine flow path formed therein. Electrode according to any.   14. The electrode according to claim 13, wherein the metal powder mixture forming step pulverizes at least three types of transition metals selected in the transition metal selecting step to a particle size of 10 µm to 200 µm.   The thin metal plate forming step presses the metal powder mixture prepared in the metal powder mixture forming step with a pressure of 500 Mpa to 800 Mpa, and has a thickness of 0.03 mm to 0.3 mm and a large number of fine particles. The electrode according to claim 13, wherein a metal sheet having a flow path formed therein is formed.   The said porous structure alloy thin plate electrode preparation process sinters the said metal thin plate at the temperature which fuse | melts the powder of the transition metal with the lowest melting point among at least three types of transition metals selected by the said transition metal selection process. An electrode according to any one of claims 13 to 15.

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