JP7193109B2 - Electrode and electrode manufacturing method - Google Patents

Description

The present invention relates to an electrode for use as an anode or a cathode, and to an electrode manufacturing method for manufacturing an electrode for use as an anode or a cathode.

A fuel cell electrode containing a platinum catalyst is disclosed in which platinum is supported on nitrogen-doped carbon obtained by calcining a porous metal complex (PCP/MOF) containing zinc, which is 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 production raw material, it contains almost no metal derived from the raw material and has a large specific surface area. can be obtained, and a highly active platinum catalyst can be obtained by supporting a small amount of platinum. Furthermore, since no metal derived from the porous metal complex (PCP/MOF), which is the raw material for production, is contained, the firing conditions can be set freely. That is, by changing the organic compound linker of the porous metal complex (PCP/MOF) used as a raw material and by adjusting the firing temperature, it is possible to control the nitrogen content and crystallinity of the obtained NDC.

JP 2018-23929 A

Various types of platinum-supported carbon are widely used as electrode catalysts for polymer electrolyte fuel cells. However, since platinum group elements are precious metals and scarce resources with a limited production amount, it is required to suppress their usage. Furthermore, development of inexpensive electrodes with non-platinum catalysts using metals other than expensive platinum is required for the future spread of polymer electrolyte fuel cells.

An object of the present invention is to provide an electrode that can be produced at low cost without using a platinum group element and that can exhibit substantially the same catalytic activity (catalytic action) as an electrode containing a platinum group element, and an electrode of the electrode. It is to provide a manufacturing method. Another object of the present invention is to be able to generate sufficient electricity in a fuel cell, supply sufficient electrical energy to a load connected to the fuel cell, and efficiently carry out electrolysis in a hydrogen gas generator. An object of the present invention is to provide an electrode capable of performing well and generating a large amount of hydrogen gas, and a method of manufacturing the electrode.

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

The feature of the electrode of the present invention in the first premise is that the electrode is a metal powder mixture in which powders of at least three transition metals selected from various transition metals are uniformly mixed and dispersed. It is formed from an alloy powder obtained by finely pulverizing the alloy molded product and a carbon electrode plate having a predetermined area on which the alloy powder is supported on both sides, and in the metal powder mixture, the work of at least three selected transition metals An electrode in which at least three transition metals are selected from among various transition metals such that the composite work function of the function approximates the work function of a platinum group element, wherein the work functions of the three transition metals are Synthetic work function has a composition (weight ratio) of 48Ni-42Cu-10Zn, 48Ni-45Mo-7Mn, 48Fe-48Ni-4Cu, 48Fe-46Ti-6Ag, 48Cu-48Fe-4Zn, or 48Cu-46Fe-6Ag The work function is equal to or higher than that of the alloy powder .

As an example of the electrode of the present invention, an alloy powder laminate porous structure is formed on both surfaces of a carbon electrode plate by alloy powders overlapping in the thickness direction of the carbon electrode plate.

As another example of the electrode of the present invention, the particle size of the transition metal powder is in the range of 10 μm to 200 μm, the particle size of the alloy powder is in the range of 10 μm to 200 μm, and the thickness of the carbon electrode plate is The dimensions are in the range 0.03 mm to 0.3 mm.

As another example of the electrode of the present invention, the metal powder mixture contains Ni (nickel) powder as a main component, and in the metal powder mixture, the work function of Ni and at least two other transitions other than Ni At least two transition metal powders other than Ni powder are selected from various transition metals so that the combined work function with the metal work function approximates the work function of the platinum group element. there is

As another example of the electrode of the present invention, the weight ratio of Ni (nickel) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and one type of electrode excluding Ni powder is used. A metal powder mixture in which the weight ratio of the transition metal powder to the total weight of the metal powder mixture is in the range of 20% to 50%, and at least one other transition metal powder excluding Ni powder. of the total weight is in the range of 3% to 20%.

As another example of the electrode of the present invention, the metal powder mixture contains Fe (iron) powder as a main component, and in the metal powder mixture, the work function of Fe and at least two other transitions excluding Fe At least two transition metal powders other than Fe powder are selected from various transition metals so that the combined work function with the metal work function approximates the work function of the platinum group element. there is

As another example of the electrode of the present invention, the weight ratio of Fe (iron) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and one type of electrode excluding Fe powder is used. A metal powder mixture in which the weight ratio of the transition metal powder to the total weight of the metal powder mixture is in the range of 20% to 50%, and at least one other transition metal powder excluding the Fe powder. of the total weight is in the range of 3% to 20%.

As another example of the electrode of the present invention, the metal powder mixture contains Cu (copper) powder as a main component, and in the metal powder mixture, the work function of Cu and at least two other transitions other than Cu At least two transition metal powders other than Cu powder are selected from various transition metals so that the combined work function with the metal work function approximates the work function of the platinum group element. there is

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

As another example of the electrode of the present invention, in the alloy molded product, at least two transition metals among the selected transition metals are melted during firing of the metal powder mixture, and the melted transition metals are used as a binder. of powder are joined together.

The second premise of the present invention for solving the above problems is an electrode manufacturing method for manufacturing electrodes used as anodes or cathodes.

The feature of the electrode manufacturing method of the present invention in the second premise is that the electrode manufacturing method is such that the composite work function of the work functions of at least three transition metals selected from various transition metals is approximate to the work function of a platinum group element. A transition metal selection step of selecting at least three types of transition metals from various transition metals, and powders of at least three types of transition metals selected by the transition metal selection step were uniformly mixed and dispersed. a metal powder mixture producing step for producing a metal powder mixture; and a metal powder compact producing step for producing a metal powder compact by applying a predetermined pressure to the metal powder mixture produced by the metal powder mixture producing step. , an alloy molded product creation step in which the metal powder compact created in the metal powder compact creation step is sintered at a predetermined temperature to form an alloy compact, and the alloy compact created in the alloy compact creation step is finely ground. An electrode manufacturing method having an alloy powder preparation step of pulverizing to produce an alloy powder, and an alloy powder supporting step of supporting the alloy powder prepared by the alloy powder preparation step on both sides of a carbon electrode plate having a predetermined area. and the composite work function of the work functions of the three transition metals is 48Ni-42Cu-10Zn, 48Ni-45Mo-7Mn, 48Fe-48Ni-4Cu, 48Fe-46Ti-6Ag, 48Cu-48Fe-4Zn, or It is equal to or higher than the work function of the alloy powder having the composition (weight ratio) of 48Cu-46Fe-6Ag .

As an example of the electrode manufacturing method of the present invention, the metal powder mixture preparation step includes pulverizing at least three transition metals selected in the transition metal selection step to a particle size of 10 μm to 200 μm, and the alloy powder preparation step. pulverizes the alloy molding to a particle size of 10 μm to 200 μm.

As another example of the electrode manufacturing method of the present invention, the metal powder compact preparation step presses the metal powder mixture prepared by the metal powder mixture preparation step at a pressure of 500 Mpa to 800 Mpa to compress the metal powder. make things

As another example of the electrode manufacturing method of the present invention, the step of preparing an alloy molded article includes forming the compacted metal powder at a temperature at which at least two transition metals among the transition metals selected in the transition metal selection step are melted. The transition metal powders are bonded using the sintered and melted transition metal as a binder.

As another example of the electrode manufacturing method of the present invention, the alloy powder supporting step includes supporting the alloy powder on both sides of a carbon electrode plate having a thickness of 0.03 mm to 0.3 mm, and An alloy powder laminated porous structure is formed on both sides of the carbon electrode plate by the overlapping alloy powder.

According to the electrode according to the present invention, an alloy molded product obtained by compressing a metal powder mixture in which at least three types of transition metal powders selected from various transition metals are uniformly mixed and dispersed and then fired is finely divided. It is formed from a pulverized alloy powder and a carbon electrode plate having a predetermined area on which the alloy powder is supported on both sides, and the composite work function of the work function of at least three selected transition metals is the work function of the platinum group element. Since at least three transition metals are selected from various transition metals so as to approximate to It can exhibit substantially the same catalytic activity (catalytic action) as an electrode containing an element, and can be suitably used as an electrode for a fuel cell or a hydrogen gas generator. The electrode is a platinum-less electrode in which the alloy molding is formed from at least three types of transition metals selected from various transition metals, and expensive platinum group elements are not used, and the electrode can be manufactured at a low cost. Since the electrode exhibits approximately the same catalytic activity (catalysis) as an electrode containing a platinum group element, the electrode can be used in a fuel cell to generate sufficient electricity in the fuel cell. In addition to being able to supply sufficient electrical energy to the load connected to the battery, by using the electrodes in a hydrogen gas generator, electrolysis can be efficiently performed and a large amount of hydrogen gas can be generated. can.

The electrode in which the alloy powder laminated porous structure is formed on both sides of the carbon electrode plate by the alloy powder overlapping in the thickness direction of the carbon electrode plate forms the alloy powder laminated porous structure on both sides of the carbon electrode plate. Therefore, the specific surface area of the alloy powder can be increased, and the catalytic action of the alloy powder can be fully utilized. It has the same work function, can exhibit substantially the same catalytic activity (catalytic action) as an electrode containing a platinum group element, and can be suitably used as an electrode for a fuel cell or a hydrogen gas generator. As for the electrode, since the electrode formed of the alloy powder laminated porous structure exhibits substantially the same catalytic activity (catalytic action) as the electrode containing the platinum group element, the use of the electrode in the fuel cell is sufficient for the fuel cell. It is possible to generate sufficient electricity and supply sufficient electrical energy to the load connected to the fuel cell, and by using the electrodes in the hydrogen gas generator, electrolysis can be performed efficiently. , can generate a large amount of hydrogen gas.

The grain size of the transition metal powder is in the range of 10 μm to 200 μm, the grain size of the alloy powder is in the range of 10 μm to 200 μm, and the thickness of the carbon electrode plate is in the range of 0.03 mm to 0.3 mm. By setting the thickness of the carbon electrode plate within the above range, the electrical resistance of the electrode can be reduced and the current can flow smoothly through the electrode. Since electrodes allow current to flow smoothly, the use of electrodes in a fuel cell can generate sufficient electricity in the fuel cell to supply sufficient electrical energy to the load connected to the fuel cell. In addition, by using the electrode in a hydrogen gas generator, electrolysis can be efficiently performed, and a large amount of hydrogen gas can be generated.

The metal powder mixture contains Ni (nickel) powder as a main component, and the composite work function of the work function of Ni and the work functions of at least two other transition metals excluding Ni is approximate to the work function of the platinum group element. Thus, the electrode in which at least two types of transition metal powders other than Ni powder are selected from various transition metals has the work function of Ni and at least two other types of transition metals other than Ni. At least two types of transition metal powders other than Ni powder are selected from various transition metals so that the combined work function with the work function of the transition metal approximates the work function of the platinum group element. Therefore, the electrode having the alloy powder or the alloy powder laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and has substantially the same catalytic activity (catalysis) as the electrode containing the platinum group element. can be exhibited, and can be suitably used as an electrode of a fuel cell or a hydrogen gas generator. In the electrode, the alloy molding is formed from Ni powder and at least two transition metal powders other than Ni powder selected from various transition metals, and expensive platinum group elements are used. It is platinum-less and can be manufactured at low cost. Electrodes exhibit substantially the same catalytic activity (catalytic action) as electrodes containing a platinum group element. Sufficient electrical energy can be supplied to the connected load, and by using the electrodes in the hydrogen gas generator, electrolysis can be efficiently performed and a large amount of hydrogen gas can be generated.

The weight ratio of Ni (nickel) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the total weight of the metal powder mixture of one type of transition metal powder excluding Ni powder is The weight ratio to the weight is in the range of 20% to 50%, and the weight ratio of at least one other transition metal powder, excluding the Ni powder, to the total weight of the metal powder mixture is 3% to 20%. A range of electrodes are selected from various transition metals such that the composite work function of the work function of Ni and the work functions of at least two other transition metals excluding Ni approximates the work function of a platinum group element. At least two types of transition metal powder other than Ni powder are selected, and the weight ratio of Ni powder and the weight ratio of at least one type of transition metal powder excluding Ni powder are selected. By setting the weight ratio of at least one other transition metal powder excluding Ni powder to the above range, the electrode having the alloy powder or the alloy powder laminated porous structure is an electrode containing a platinum group element It has almost the same work function as that of an electrode containing a platinum group element, and can exhibit almost the same catalytic activity (catalytic action) as an electrode containing a platinum group element. It is possible to supply sufficient electrical energy to the load connected to the fuel cell, and by using the electrodes in the hydrogen gas generator, electrolysis can be performed efficiently, and a large amount of hydrogen can be produced. Gas can be generated.

The metal powder mixture is mainly composed of Fe (iron) powder, and the combined work function of the work function of Fe and the work function of at least two other transition metals excluding Fe is approximate to the work function of the platinum group element Thus, the electrode in which at least two types of transition metal powders other than Fe powder are selected from various transition metals has the work function of Fe and at least two other types of metals other than Fe. At least two types of transition metal powders other than Fe powder are selected from various transition metals so that the combined work function with the work function of the transition metal approximates the work function of the platinum group element. Therefore, the electrode having the alloy powder or the alloy powder laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and has substantially the same catalytic activity (catalysis) as the electrode containing the platinum group element. can be exhibited, and can be suitably used as an electrode of a fuel cell or a hydrogen gas generator. In the electrode, the alloy molding is formed from Fe powder and at least two transition metal powders other than Fe powder selected from various transition metals, and expensive platinum group elements are used. It is platinum-less and can be manufactured at low cost. Electrodes exhibit substantially the same catalytic activity (catalytic action) as electrodes containing a platinum group element. Sufficient electrical energy can be supplied to the connected load, and by using the electrodes in the hydrogen gas generator, electrolysis can be efficiently performed and a large amount of hydrogen gas can be generated.

The weight ratio of Fe (iron) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the entire metal powder mixture of one type of transition metal powder excluding Fe powder The weight ratio to the weight is in the range of 20% to 50%, and the weight ratio of at least one other transition metal powder, excluding the Fe powder, to the total weight of the metal powder mixture is 3% to 20%. A range of electrodes are selected from various transition metals such that the combined work function of the work function of Fe and the work functions of at least two other transition metals excluding Fe approximates the work function of a platinum group element. At least two transition metal powders other than the Fe powder are selected, and the weight ratio of the Fe powder and the weight ratio of the at least one transition metal powder excluding the Fe powder are selected. By setting the weight ratio of the powder of at least one other transition metal excluding the powder of Fe to the above range, the electrode having the alloy powder or the alloy powder laminated porous structure is an electrode containing a platinum group element It has almost the same work function as that of an electrode containing a platinum group element, and can exhibit almost the same catalytic activity (catalytic action) as an electrode containing a platinum group element. It is possible to supply sufficient electrical energy to the load connected to the fuel cell, and by using the electrodes in the hydrogen gas generator, electrolysis can be performed efficiently, and a large amount of hydrogen can be produced. Gas can be generated.

The metal powder mixture is mainly composed of Cu (copper) powder, and the combined work function of the work function of Cu and the work function of at least two other transition metals excluding Cu is approximate to the work function of the platinum group element Thus, the electrode in which at least two transition metal powders other than Cu powder are selected from various transition metals has the work function of Cu and at least two other types of transition metals other than Cu. At least two types of transition metal powders other than Cu powder are selected from among various transition metals so that the composite work function with the work function of the transition metal approximates the work function of the platinum group element. Therefore, the electrode having the alloy powder or the alloy powder laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and has substantially the same catalytic activity (catalysis) as the electrode containing the platinum group element. can be exhibited, and can be suitably used as an electrode of a fuel cell or a hydrogen gas generator. In the electrode, the alloy molding is formed from Cu powder and at least two transition metal powders other than Cu powder selected from various transition metals, and expensive platinum group elements are used. It is platinum-less and can be manufactured at low cost. Electrodes exhibit substantially the same catalytic activity (catalytic action) as electrodes containing a platinum group element. Sufficient electrical energy can be supplied to the connected load, and by using the electrodes in the hydrogen gas generator, electrolysis can be efficiently performed and a large amount of hydrogen gas can be generated.

The weight ratio of Cu (copper) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the entire metal powder mixture of one type of transition metal powder excluding Cu powder The weight ratio is in the range of 20% to 50%, and the weight ratio of at least one other transition metal powder, excluding Cu powder, to the total weight of the metal powder mixture is 3% to 20%. A range of electrodes are selected from various transition metals such that the combined work function of the work function of Cu and the work functions of at least two other transition metals excluding Cu approximates the work function of a platinum group element. At least two types of transition metal powder other than Cu powder are selected, and the weight ratio of Cu powder and the weight ratio of at least one type of transition metal powder excluding Cu powder are selected. , the weight ratio of the powder of at least one other transition metal excluding the powder of Cu is within the above range, so that the electrode having the alloy powder or the alloy powder laminated porous structure contains a platinum group element It has almost the same work function as that of an electrode containing a platinum group element, and can exhibit almost the same catalytic activity (catalytic action) as an electrode containing a platinum group element. It is possible to supply sufficient electrical energy to the load connected to the fuel cell, and by using the electrodes in the hydrogen gas generator, electrolysis can be performed efficiently, and a large amount of hydrogen can be produced. Gas can be generated.

At least two transition metals among the selected transition metals are melted during firing of the metal powder mixture, and the electrode in which the transition metal powders are bonded using the melted transition metals as a binder is made of transition metals. An alloy molded product can be made by melting at least two kinds of transition metals of, and an alloy powder can be made by finely pulverizing the alloy molded product, and an alloy powder or an alloy powder laminated porous structure can be produced. It is possible to make an electrode with The electrode has substantially the same work function as the electrode containing the platinum group element, and has substantially the same catalytic activity (catalysis) as the electrode containing the platinum group element. By using the electrodes in the fuel cell, sufficient electricity can be generated in the fuel cell, sufficient electrical energy can be supplied to the load connected to the fuel cell, and the electrodes is used in the hydrogen gas generator, electrolysis can be efficiently performed, and a large amount of hydrogen gas can be generated.

According to the electrode manufacturing method according to the present invention, among various transition metals, the composite work function of the work functions of at least three transition metals selected from various transition metals is approximated to the work function of the platinum group element. a transition metal selection step of selecting at least three types of transition metals from a metal powder compact creation step of pressurizing the metal powder mixture created by the metal powder mixture creation step at a predetermined pressure to form a metal powder compact, and a metal powder compact creation step. An alloy molded product making process for making an alloy molded product by firing the compressed metal powder at a predetermined temperature, and an alloy powder for making the alloy powder by pulverizing the alloy molded product made by the alloy molded product making process. Since the electrode is manufactured by each process of the body preparation process and the alloy powder support process in which the alloy powder prepared in the alloy powder preparation process is supported on both sides of a carbon electrode plate having a predetermined area, platinum group elements are used. It is possible to make a platinum-less electrode at a low cost, and it is possible to fully and reliably utilize the catalytic function, and it has excellent catalytic activity (catalytic action) and is suitable for fuel cells and hydrogen gas generators. Electrodes can be made that can be used.

The metal powder mixture preparation step pulverizes at least three transition metals selected by the transition metal selection step to a particle size of 10 μm to 200 μm, and the alloy powder preparation step pulverizes the alloy molding to a particle size of 10 μm to 200 μm. In the method of manufacturing an electrode by pulverizing, an alloy molded product can be produced by pulverizing the transition metal to a particle size within the above range, and the alloy molded product is pulverized to a particle size within the above range to obtain an alloy powder. Alternatively, it is possible to make a platinum-less electrode having an alloy powder laminated porous structure, and it is possible to fully and reliably utilize the catalytic function, and it has excellent catalytic activity (catalytic action). Electrodes can be made that are suitable for use in hydrogen gas generators.

The electrode manufacturing method in which the metal powder compact creation step pressurizes the metal powder mixture produced by the metal powder mixture creation step at a pressure of 500 Mpa to 800 Mpa to make the metal powder compact, comprises: By pressing (compressing) within a range of pressure, a metal powder compact can be produced, and the metal powder compact can be sintered to produce an alloy molded product, and the alloy molded product can be pulverized. Platinum-less electrodes can be made with solid alloy powders or alloy powder laminated porous structures.

The metal powder compact is fired at a temperature at which at least two types of transition metals selected in the transition metal selection step are melted in the alloy molded product creation step, and the transition metals are combined with the melted transition metals as a binder. In the electrode manufacturing method for joining powders, at least two kinds of transition metals out of the transition metals are melted to form an alloy molded product, and the alloy molded product is pulverized to produce an alloy powder. It is possible to make platinum-less electrodes with alloy powders or alloy powder laminated porous structures.

In the alloy powder supporting step, the alloy powder is supported on both sides of a carbon electrode plate having a thickness of 0.03 mm to 0.3 mm, and the alloy powder is deposited on both sides of the carbon electrode plate by the alloy powder overlapping in the thickness direction of the carbon electrode plate. The electrode manufacturing method for forming the body laminated porous structure can produce a platinum-less electrode having the alloy powder laminated porous structure with an increased specific surface area of the alloy powder, and the thickness dimension of the carbon electrode plate can be adjusted as described above. By setting it within the range, the electrical resistance of the electrode can be reduced, and a platinum-less electrode that allows current to flow smoothly can be produced.

The perspective view of the electrode shown as an example. FIG. 2 is a partially enlarged front view of an electrode; FIG. 3 is an end view on line AA of FIG. 2; The partial enlarged front view of the electrode shown as another example. FIG. 5 is an end view of line BB of FIG. 4; FIG. 2 is an exploded perspective view showing an example of a cell using electrodes; Side view of a cell using electrodes. FIG. 4 is a diagram for explaining power generation of a fuel cell (polymer electrolyte fuel cell) using electrodes. The figure which shows the result of the electromotive force test of an electrode. FIG. 4 is a diagram showing results of an IV characteristic test of electrodes; The figure explaining the electrolysis of the hydrogen gas generator which uses an electrode. 4A and 4B are diagrams for explaining a method for manufacturing an electrode;

The details of the electrode according to the present invention will now be described with reference to the accompanying drawings, such as FIG. 1, which is a perspective view of the electrode 10A shown by way of example. 2 is a partially enlarged front view of the electrode 10A, and FIG. 3 is an end view taken along line AA of FIG. In FIG. 1, arrow X indicates the thickness direction, and arrow Y indicates the radial direction.

The electrode 10A is used as an anode or a cathode, and is used as an electrode (catalyst) of the fuel cell 21 (see FIG. 6) or an electrode (catalyst) of the hydrogen gas generator 30 (see FIG. 11). . The electrode 10A has a front surface 11 and a rear surface 12, has a predetermined area and a predetermined thickness, and has a rectangular planar shape. The planar shape of the electrode 10A (including the electrode 10B) is not particularly limited, and can be formed into any other planar shape such as a circle, an ellipse, a polygon, etc., in addition to the square shape, depending on the application.

The electrode 10A is formed from an alloy powder 13 (alloy powder) and a carbon electrode plate 14 having a predetermined area. The alloy powder 13 is made by pulverizing an alloy molding 42 (alloy molding) (see FIG. 12). The alloy powder 13 has a particle size in the range of 10 μm to 200 μm. The alloy molding 42 is a metal powder mixture 40 (see FIG. 12) obtained by uniformly mixing and dispersing powders of at least three transition metals selected from various transition metals processed into powder (pulverized). It is made by firing (sintering) after compressing. As transition metals, 3d transition metals and 4d transition metals are used. Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), and Zn (zinc) are used as 3d transition metals. Nb (niobium), Mo (molybdenum), and Ag (silver) are used as 4d transition metals.

The transition metal powder includes Ti (titanium) powder processed into powder (pulverized), Cr (chromium) powder processed into powder (pulverized), and powdered (pulverized). Mn (manganese) powder processed into powder (finely ground) Fe (iron) powder processed into powder (finely ground) Co (cobalt) powder processed into powder (finely ground) ) Ni (nickel) powder processed into powder (finely ground) Cu (copper) powder processed into powder (finely ground) Zn (zinc) powder processed into powder (finely ground) Pulverized) Nb (niobium) powder, Mo (molybdenum) powder processed into powder (pulverized), and Ag (silver) powder processed into powder are used.

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

In the metal powder mixture 40, the transition metals are selected such that the composite work function of the work function (the energy required to extract an electron from the material) of the at least three selected transition metals approximates the work function of the platinum group elements. At least three transition metals are selected from 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). Note that the work function of platinum is 5.65 (eV).

As an example of the metal powder mixture 40, the main component is Ni (nickel) powder processed (pulverized) into powder, and the Ni powder and Ni are processed (pulverized) into powder excluding Ni powder. At least two other transition metals (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Fe (iron), powder Co (cobalt), powder at least two of powdery Cu (copper), powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver)) powder The metal powder mixture 40 is uniformly mixed and dispersed.

A metal powder mixture 40 obtained by mixing powder of Ni (nickel) as a main component and powder of at least two other transition metals excluding Ni has a work function of Ni and at least two other metals excluding Ni. At least two types of transition metal powders other than Ni powder are selected from various transition metals so that the combined work function with the work function of the transition metal approximates the work function of the platinum group element. It is

In the alloy molded product 42 containing Ni powder as a main component, at least two transition metals among the selected transition metals are melted during firing of the metal powder mixture 40, and the melted transition metals are used as a binder. Metal powder is bonded. The alloy powder 13 containing Ni as a main component is obtained by pulverizing an alloy molded product 42 produced by compressing and then firing a metal powder mixture 40 containing Ni powder as a main component, and the particle size is from 10 μm to 10 μm. It is a finely pulverized product of 200 μm.

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

As a specific example of the alloy powder 13 containing Ni (nickel) as a main component (an alloy powder containing Ni as a main component), Ni powder, Cu powder, and ZN powder are uniformly mixed and dispersed. The metal powder mixture 40 is compressed and then fired to form an alloy molded product 42. The alloy molded product 42 is pulverized to a finely pulverized product having a particle size of 10 μm to 200 μm. This alloy powder 13 has a Ni powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40, a Cu powder weight ratio of 42% with respect to the total weight of the metal powder mixture 40, The powder weight ratio of Zn to the total weight of 40 is 10%. Since the melting point of Ni is 1455° C., the melting point of Cu is 1084.5° C., and the melting point of Zn is 419.85° C., the Zn powder and Cu powder are melted, and the melted Zn and Cu act as a binder. Ni powder is joined by

As another specific example of the alloy powder 13 containing Ni (nickel) as a main component, a metal powder mixture 40 in which Ni powder, Mn powder, and Mo powder are uniformly mixed and dispersed is compressed. After firing, an alloy molding 42 is produced, and the alloy molding 42 is pulverized to a finely pulverized product having a particle size of 10 μm to 200 μm. This alloy powder 13 has a Ni powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40, and a Mn powder weight ratio of 7% with respect to the total weight of the metal powder mixture 40. The powder weight ratio of Mo to the total weight of 40 is 45%. Since the melting point of Ni is 1455° C., the melting point of Mn is 1246° C., and the melting point of Mo is 2623° C., the Mn powder and the Ni powder are melted, and the melted Mn and Ni become a binder to form the Mo powder. joins the body.

As another example of the metal powder mixture 40, the main component is Fe (iron) powder that has been processed (pulverized) into powder, and the powder of Fe and the powder excluding Fe are processed (pulverized) into powder. At least two other transition metals (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Co (cobalt), powder Ni (nickel) , powdery Cu (copper), powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver)) powder and are uniformly mixed and dispersed.

A metal powder mixture 40 obtained by mixing powder of Fe (iron) as a main component and powder of at least two other transition metals excluding Fe has a work function of Fe and at least two other metals excluding Fe. At least two types of transition metal powders other than Fe powder are selected from among various transition metals so that the composite work function with the work function of the transition metal is approximate to the work function of the platinum group element It is

In the alloy molded product 42 containing Fe powder as a main component, at least two transition metals among the selected transition metals are melted during firing of the metal powder mixture 40, and the melted transition metals are used as a binder. Metal powder is bonded. The alloy powder 13 containing Fe as the main component is obtained by pulverizing the alloy molded product 42 produced by compressing and then firing the metal powder mixture 40 containing Fe powder as the main component, and the particle size is from 10 μm to 10 μm. It is a finely pulverized product of 200 μm.

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

As a specific example of the alloy powder 13 containing Fe (iron) as a main component (alloy powder containing Fe as a main component), Fe powder, Ni powder, and Cu powder are uniformly mixed and dispersed. The metal powder mixture 40 is compressed and then fired to form an alloy molded product 42. The alloy molded product 42 is pulverized to a finely pulverized product having a particle size of 10 μm to 200 μm. This alloy powder 13 has a Fe powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40, and a Ni powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40. The powder weight ratio of Cu to the total weight of 40 is 4%. Since the melting point of Fe is 1536° C., the melting point of Ni is 1455° C., and the melting point of Cu is 1084.5° C., the powder of Cu and the powder of Ni are melted, and the melted Cu and Ni become a binder to form Fe of powder are joined together.

As another specific example of the alloy powder 13 containing Fe (iron) as a main component, a metal powder mixture 40 obtained by uniformly mixing and dispersing Fe powder, Ti powder, and Ag powder is compressed. After firing, an alloy molding 42 is produced, and the alloy molding 42 is pulverized to a finely pulverized product having a particle size of 10 μm to 200 μm. This alloy powder 13 has a Fe powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40, a Ti powder weight ratio of 46% with respect to the total weight of the metal powder mixture 40, The powder weight ratio of Ag to the total weight of 40 is 6%. Since the melting point of Fe is 1536° C., the melting point of Ti is 1666° C., and the melting point of Ag is 961.93° C., the Ag powder and the Fe powder are melted, and the melted Ag and Fe become a binder to form Ti. of powder are joined together.

As another example of the metal powder mixture 40, the main component is Cu (copper) powder that has been processed (pulverized) into powder, and the powder of Cu and the powder excluding Cu are processed (pulverized). Other transition metals (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Fe (iron), powder Co (cobalt), powder Ni (nickel), powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), and powdery Ag (silver)) are uniformly mixed. It is a metal powder mixture 40 mixed and dispersed.

A metal powder mixture 40 obtained by mixing powder of Cu (copper) as a main component and powder of at least two kinds of transition metals other than Cu has a work function of Cu and at least two other kinds of metals other than Cu. At least two types of transition metal powders other than Cu powder are selected from among various transition metals so that the composite work function with the work function of the transition metal is approximate to the work function of the platinum group element. It is

In the alloy molded product 42 containing Cu powder as a main component, at least two transition metals among the selected transition metals are melted during firing of the metal powder mixture 40, and the melted transition metals are used as a binder. Metal powder is bonded. The alloy powder containing Cu as the main component has a particle size of 10 μm to 200 μm, which is obtained by pulverizing the alloy molding 42 produced by compressing and then firing the metal powder mixture 40 containing Cu powder as the main component. It is a finely ground product of

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

As a specific example of the alloy powder 13 containing Cu (copper) as a main component (alloy powder containing Cu as a main component), Cu powder, Fe powder, and Zn powder are uniformly mixed and dispersed. The metal powder mixture 40 is compressed and then fired to form an alloy molded product 42. The alloy molded product 42 is pulverized to a finely pulverized product having a particle size of 10 μm to 200 μm. This alloy powder 13 has a Cu powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40, and a Fe powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40. The powder weight ratio of Zn to the total weight of 40 is 4%. Since Cu has a melting point of 1084.5° C., Fe has a melting point of 1536° C., and Zn has a melting point of 419.58° C., the Zn powder and Cu powder are melted, and the melted Zn and Cu act as a binder. Fe powder is joined by

As another specific example of the alloy powder 13 mainly composed of Cu (copper), a metal powder mixture 40 in which Cu powder, Fe powder, and Ag powder are uniformly mixed and dispersed is compressed. After firing, an alloy molding 42 is produced, and the alloy molding 42 is pulverized to a finely pulverized product having a particle size of 10 μm to 200 μm. The alloy powder 13 has a Cu powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40, and a Fe powder weight ratio of 46% with respect to the total weight of the metal powder mixture 40. The powder weight ratio of Ag to the total weight of 40 is 6%. Since Cu has a melting point of 1084.5° C., Fe has a melting point of 1536° C., and Ag has a melting point of 961.93° C., the Ag powder and the Cu powder are melted, and the melted Ag and Cu act as a binder. Fe powder is joined by

The carbon electrode plate 14 has a front surface 15 and a rear surface 16, has a predetermined area and a predetermined thickness L1, and has a rectangular planar shape. The planar shape of the carbon electrode plate 14 is not particularly limited, and it can be formed in any other planar shape such as a circle, an ellipse, a polygon, etc., in addition to the square. As an example of the carbon electrode plate 14, carbon graphite (graphite) powder having a size of several μm to several tens of μm and a conductive binder (conductive binding material) are formed by cold isostatic pressing and then graphitized at about 3000°C. A sheet-like electrode material is used. As another example of the carbon electrode plate 14, carbon graphite (graphite) powder having a size of several μm to several tens of μm and a conductive binder (conductive binding material) are extruded from an extrusion die and then graphitized at about 3000°C. A sheet-like electrode material is used. Glassy carbon can also be used as the carbon electrode plate 14 .

The carbon electrode plate 14 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. As shown in FIG. 3, a plurality of alloy powders 13 are carried on the entire front surface 15 and the rear surface 16 of the carbon electrode plate 14 (both surfaces). The alloy powder 13 is carried on the entire front surface 15 and the rear surface 16 (both sides) of the carbon electrode plate 14 by means of a conductive binder (conductive binding material) or plasma spraying.

If the thickness dimension L1 of the carbon electrode plate 14 is less than 0.03 mm, its strength is reduced, and the carbon electrode plate 14 (electrode 10A (or electrode 10B)) is easily broken or damaged when an impact is applied. It may not be able to maintain its shape. When the thickness dimension L1 of the carbon electrode plate 14 exceeds 0.3 mm, the electrical resistance of the carbon electrode plate 14 (electrode 10A (or electrode 10B)) increases, and the carbon electrode plate 14 (electrode 10A (or electrode 10B)) If the current does not flow smoothly and the fuel cell 21 cannot generate enough electricity when the electrode 10A (or electrode 10B) is used in the fuel cell 21, the load connected to the fuel cell 21 will not generate enough electricity. Inability to supply electrical energy. In addition, when the electrode 10A (or the electrode 10B) is used in the hydrogen gas generator 30, the electrolysis cannot be performed efficiently, and the hydrogen gas generator 30 cannot generate a large amount of hydrogen gas in a short time. Can not.

Since the carbon electrode plate 14 has a thickness dimension L1 in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm, the carbon electrode plate 14 (electrode 10A (or electrode 10B)) has high strength and can maintain its shape, and can prevent breakage or damage of the carbon electrode plate 14 when an impact is applied to the carbon electrode plate 14 . Furthermore, by setting the thickness dimension L1 within the above range, the electrical resistance of the carbon electrode plate 14 (electrode 10A (or electrode 10B)) can be reduced, and the carbon electrode plate 14 (electrode 10A (or electrode 10B)) can be The current flows smoothly, and when the electrode 10A is used in the fuel cell 21, sufficient electricity can be generated in the fuel cell 21, and sufficient electrical energy can be supplied to the load connected to the fuel cell 21. can. Moreover, when the electrode 10A is used in the hydrogen gas generator 30, electrolysis can be efficiently performed, and a large amount of hydrogen gas can be generated in the hydrogen gas generator 30 in a short time.

FIG. 4 is a partially enlarged front view of an electrode 10B shown as another example, and FIG. 5 is a BB line end view of FIG. The electrode 10B differs from the electrode 10A in FIG. 1 in that the alloy powder laminated porous structure 17 is formed by a plurality of alloy powders 13 overlapping in the thickness direction of the carbon electrode plate 14 so that the front surface 15 and the rear surface 16 (both sides) of the carbon electrode plate 14 are formed. ), and other configurations are the same as those of the electrode 10A in FIG. A detailed description of other configurations of 10B is omitted.

The electrode 10B is used as an anode or a cathode, and is used as an electrode (catalyst) of the fuel cell 21 (see FIG. 6) or an electrode (catalyst) of the hydrogen gas generator 30 (see FIG. 11). . The electrode 10B has a front surface 11 and a rear surface 12, has a predetermined area and a predetermined thickness, and has a rectangular planar shape. The electrode 10B is formed of an alloy powder 13 (alloy powder) and a carbon electrode plate 14 having a predetermined area and carrying the alloy powder 13 on both surfaces (front and rear surfaces 15 and 16).

The entire area of the front surface 15 and the entire area of the rear surface 16 (entire area of both surfaces) of the carbon electrode plate 14 are covered with a plurality of alloy powders 13 overlapping (stacked) in the thickness direction of the carbon electrode plate 14 to form an alloy powder laminate porous structure. A structure 17 is formed. The alloy powder 13 is made by pulverizing an alloy compact 42 (alloy compact). The alloy molding 42 is fired after compressing a metal powder mixture 40 in which powders of at least three kinds of transition metals selected from various transition metals processed into powder (pulverized) are uniformly mixed and dispersed. It is made from (sintering). The transition metal, metal powder mixture 40, alloy molding 42, and alloy powder 13 are the same as those of the electrode 10A of FIG. The particle size of the transition metal powder, the particle size of the alloy powder 13, and the thickness dimension L1 of the carbon electrode plate 14 are the same as those of the electrode 10A in FIG.

A large number of fine flow paths 18 (passage holes) having different diameters are formed in the alloy powder laminate porous structure 17 . A gas (hydrogen gas or oxygen gas) or a liquid (water) flows through the flow paths 18 (passage holes). These flow paths 18 (passage holes) have a plurality of flow holes 19 that open on the front surface 15 side of the carbon electrode plate 14 and a plurality of flow holes 19 that open on the rear surface 16 side of the carbon electrode plate 14 . , and penetrates the alloy powder laminate porous structure 17 toward the front surface 11 of the electrode 10B and penetrates the alloy powder laminate porous structure 17 toward the rear surface 12 of the electrode 10B.

The flow paths 18 extend while irregularly bending in the thickness direction of the carbon electrode plate 14, and also irregularly bend in the radial direction of the carbon electrode plate 14 toward the center from the outer peripheral edge of the carbon electrode plate 14. It's getting longer. The flow paths 18 that are adjacent to each other in the radial direction of the carbon electrode plate 14 and extend in a curved manner in the thickness direction are partially connected in the radial direction, and one flow path 18 and the other flow path 18 are in communication with each other. The channels 18 that are adjacent to each other in the thickness direction of the carbon electrode plate 14 and bend in the radial direction are partially connected in the thickness direction, and one channel 18 and the other channel 18 communicate with each other.

The opening areas (opening diameters) of the channels 18 (passage holes) are not uniform in the thickness direction of the carbon electrode plate 14, but vary irregularly in the thickness direction. is not uniform in the radial direction, but varies irregularly in the radial direction. The flow paths 18 are irregularly opened in the thickness direction and the radial direction while their opening areas (opening diameters) increase and decrease. Further, the opening areas (opening diameters) of the flow openings 19 that open to the front surface 11 and the flow openings 19 that open to the rear surface 12 are not uniform and differ. The opening diameter of the channel 18 (passage hole) and the opening diameter of the flow port 19 are in the range of 1 μm to 100 μm.

The alloy powder laminated porous structure 17 has a porosity in the range of 15% to 30% and a relative density in the range of 70% to 85%. When the porosity of the alloy powder laminate porous structure 17 is less than 15% and the relative density exceeds 85%, a large number of fine flow paths 18 (passage holes) are formed in the alloy powder laminate porous structure 17. Therefore, the specific surface area of the alloy powder laminate porous structure 17 cannot be increased. If the porosity of the alloy powder laminated porous structure 17 exceeds 30% and the relative density is less than 70%, the opening area (opening diameter) of the flow path 18 (passage hole) becomes larger than necessary, and the alloy powder The strength of the laminated porous structure 17 is lowered, and the alloy powder laminated porous structure 17 may easily break or break when an impact is applied, and may not be able to maintain its shape.

Since the porosity and relative density of the alloy powder laminate porous structure 17 are within the above ranges, the alloy powder laminate porous structure 17 has a large number of fine flow paths 18 (passage holes) having different opening areas (opening diameters). ), and the specific surface area of the alloy powder laminate porous structure 17 can be increased. The contact surface of the structure 17 (the surface of the alloy powder 13) can be widely contacted.

The alloy powder laminated porous structure 17 has a density in the range of 5.0 g/cm ² to 7.0 g/cm ² . When the density of the alloy powder-layered porous structure 17 is less than 5.0 g/cm ² , the strength of the alloy powder-layered porous structure 17 is lowered, and the alloy powder-layered porous structure 17 does not become strong when an impact is applied. It breaks or breaks easily and may not be able to maintain its shape. When the density of the alloy powder-layered porous structure 17 exceeds 7.0 g/cm ² , many fine flow paths 18 (passage holes) are not formed in the alloy powder-layered porous structure 17, and the alloy powder layer The specific surface area of the porous structure 17 cannot be increased.

The alloy powder laminate porous structure 17 formed on both surfaces (front and rear surfaces 15 and 16) of the carbon electrode plate 14 has a density within the above range. It is possible to increase the specific surface area of the alloy powder laminated porous structure 17, which is formed into a porous structure having channels 18 (passage holes). The liquid can be brought into wide contact with the contact surface of the alloy powder laminated porous structure 17 (the surface of the alloy powder 13).

If the particle size of the transition metal powder is less than 10 μm, the flow path 18 (passage hole) is blocked by the transition metal, and a large number of fine flow paths 18 may be formed in the alloy powder laminated porous structure 17 . Therefore, the specific surface area of the alloy powder laminate porous structure 17 cannot be increased. When the particle size of the transition metal powder exceeds 200 μm, the opening area (opening diameter) of the flow path 18 (passage hole) becomes larger than necessary, and many fine flow paths occur in the alloy powder laminated porous structure 17. The path 18 cannot be formed, and the specific surface area of the alloy powder laminated porous structure 17 cannot be increased. Since the particle size of the transition metal powder is within the above range, the alloy powder laminate porous structure 17 is molded into a porous structure having a large number of fine flow passages 18 (passage holes). The specific surface area of the material 17 can be increased, and while the gas or liquid flows through the flow paths 18, the gas or liquid is widely in contact with the contact surface of the alloy powder laminated porous structure 17 (surface of the alloy powder 13). can be made

FIG. 6 is an exploded perspective view showing an example of a cell 20 using electrodes 10A and 10B, and FIG. 7 is a side view of cell 20 using electrodes 10A and 10B. FIG. 8 is a diagram illustrating power generation of a fuel cell 21 (polymer electrolyte fuel cell) using the electrodes 10A and 10B, and FIG. 9 is a diagram illustrating the results of an electromotive voltage test of the electrodes 10A and 10B. . FIG. 10 is a diagram showing the results of the IV characteristic test of electrodes 10A and 10B.

As an example of the cell 20 using the electrode 10A or the electrode 10B, as shown in FIG. cathode), a solid polymer electrolyte membrane 24 (fluorinated ion exchange membrane having a sulfonic acid group) interposed between the fuel electrode 22 and the air electrode 23, and a separator 25a (bipolar plate) and a separator 25b (bipolar plate) located outside the air electrode 23 in the thickness direction. The separators 25a and 25b are engraved with supply channels for reactant gases (hydrogen, oxygen, etc.).

In the cell 20, as shown in FIG. 7, the fuel electrode 22, the air electrode 23, and the solid polymer electrolyte membrane 24 are overlapped and integrated in the thickness direction to form a membrane electrode assembly (MEA), The membrane/electrode assembly is sandwiched between the separators 25a and 25b. The solid polymer electrolyte membrane 24, the fuel electrode 22 (the electrode 10A or the electrode 10B) and the air electrode 23 (the electrode 10A or the electrode 10B) are laminated by hot pressing, and the solid polymer electrolyte membrane 24 and the alloy powder 13 are laminated. overlaps without gaps, and the solid polymer electrolyte membrane 24 and the alloy powder 13 are closely attached without gaps, or the solid polymer electrolyte membrane 24 and the alloy powder laminated porous structure 17 overlap without gaps, and the solid polymer electrolyte The film 24 and the alloy powder laminated porous structure 17 are in close contact with each other without a gap. In the fuel cell 21 (polymer electrolyte fuel cell), a plurality of cells 20 (single cells) are stacked in one direction, and the cells 20 are connected in series to form a cell stack (fuel cell stack). The solid polymer electrolyte membrane 25 has proton conductivity and no electronic conductivity.

A gas diffusion layer 26a is formed between the fuel electrode 22 and the separator 25a, and a gas diffusion layer 26b is formed between the air electrode 23 and the separator 25b. A gas seal 27a is installed above and below the gas diffusion layer 26a between the fuel electrode 22 and the separator 25a. A gas seal 27b is installed above and below the gas diffusion layer 26b between the air electrode 23 and the separator 25b.

In the fuel cell 21 (polymer electrolyte fuel cell), as shown in FIG. 8, hydrogen (fuel) is supplied to the fuel electrode 22 (electrode 10A or electrode 10B), and hydrogen (fuel) is supplied to the air electrode 23 (electrode 10A or electrode 10B). Air (oxygen) is supplied. At the fuel electrode 22, hydrogen is decomposed into protons (hydrogen ions, H ⁺ ) and electrons by the reaction (catalysis) of H ₂ →2H ⁺ +2e ⁻ . After that, protons move through the solid polymer electrolyte membrane 24 to the air electrode 23 , and electrons move through the conducting wire 28 to the air electrode 23 . Protons generated at the fuel electrode 22 flow through the solid polymer electrolyte membrane 24 . At the air electrode 23, the protons transferred from the solid polymer electrolyte membrane 24 and the electrons transferred through the conducting wire 28 react with oxygen in the air, and water is produced by the reaction 4H ⁺ +O ₂ +4e→2H ₂ O.

at least three transition metals are selected from among the transition metals such that the composite work function of the work functions of the at least three transition metals approximates the work function of the platinum group element, and the selected at least three transition metals are The alloy powder 13 made from is supported on both surfaces (front and rear surfaces 15, 16) of the carbon electrode plate 14, and the alloy powder 13 and the alloy powder laminated porous structure 17 are attached to the fuel electrode 22 (electrode 10A or electrode 10B). Since the fuel electrode 22 and the air electrode 23 (the electrode 10A or the electrode 10B) are configured, the fuel electrode 22 and the air electrode 23 exhibit excellent catalytic activity (catalytic action), and hydrogen is efficiently decomposed into protons and electrons.

In the electromotive voltage test, the voltage (V) between the fuel electrode 22 and the air electrode 23 (between the electrodes 10A and 10B) was measured for 15 minutes after the hydrogen gas was injected. In FIG. 9, which shows the results of the electromotive voltage test, the horizontal axis represents the measurement time (min), and the vertical axis represents the voltage (V) between the electrodes. In a polymer electrolyte fuel cell using an electrode (platinum electrode) utilizing (supporting) a platinum group element (platinum electrode), as can be seen from FIG. The voltage was around 1.079 (V). On the other hand, in the polymer electrolyte fuel cell 21 using the fuel electrode 22 (platinum-less electrodes 10A and 10B) and the air electrode 23 (platinum-less electrodes 10A and 10B), between the fuel electrode 22 and the air electrode 23 The voltage (electromotive force) of was 1.01 (V) to 1.02 (V).

In the IV characteristic test, a load 29 was connected between the fuel electrode 22 and the air electrode 23 (between the electrodes 10A and between the electrodes 10B) to measure the relationship between voltage and current. In FIG. 10, which shows the results of the IV characteristic test, the horizontal axis represents current (A) and the vertical axis represents voltage (V). In the polymer electrolyte fuel cell 21 using the fuel electrode 22 (platinum-less electrodes 10A, 10B) and the air electrode 23 (platinum-less electrodes 10A, 10B), it can be seen from FIG. 10 showing the results of the IV characteristic test. As can be seen, the voltage drop rate was not significantly different from that of polymer electrolyte fuel cells using electrodes (platinum electrodes) utilizing (supporting) a platinum group element. As shown in the results of the electromotive voltage test in FIG. 9 and the results of the IV characteristic test in FIG. 10, the platinum-less fuel electrode 22 and the air electrode 23, which do not use platinum group elements, emit electrons to produce hydrogen ions. It was confirmed that it has an excellent catalytic action that promotes the reaction and has an oxygen reduction function (catalytic action) that is substantially the same as an electrode using platinum.

FIG. 11 is a diagram illustrating electrolysis of hydrogen gas generator 30 using electrodes 10A and 10B. An example of a hydrogen gas generator 30 using electrodes 10A and 10B, as shown in FIG. ), a solid polymer electrolyte membrane 33 (fluorinated ion exchange membrane having a sulfonic acid group) interposed between the anode 31 and the cathode 32, an anode power supply member 34 and a cathode power supply member 35, an anode water tank 36 and It is formed of a cathode water reservoir 37 , an anode main electrode 38 and a cathode main electrode 39 . The hydrogen gas generator 30 supplies electricity to the anode 31 and the cathode 32, causing an oxidation reaction at the anode 31 and a reduction reaction at the cathode 32, thereby chemically decomposing water.

In the hydrogen gas generator 30, the anode 31, the cathode 32, and the solid polymer electrolyte membrane 33 are superimposed and integrated in the thickness direction to form a membrane electrode assembly (MEA). An anode power supply member 34 and a cathode power supply member 35 are sandwiched between them. The solid polymer electrolyte membrane 33, the anode 31 (the electrode 10A or the electrode 10B) and the cathode 32 (the electrode 10A or the electrode 10B) are laminated by hot pressing, and the solid polymer electrolyte membrane 33 and the alloy powder 13 are laminated without gaps. They are overlapped, or the solid polymer electrolyte membrane 22 and the alloy powder laminated porous structure 17 are overlapped without gaps. The solid polymer electrolyte membrane 33 has proton conductivity and no electronic conductivity.

The anode power supply member 34 is positioned outside the anode 31 and is in close contact with the anode 31 to supply positive current to the anode 31 . The anode water tank 36 is located outside the anode power supply member 34 and is in close contact with the anode power supply member 34 . The anode main electrode 38 is located outside the anode water tank 36 and supplies positive current to the anode power supply member 34 . The cathode power supply member 35 is positioned outside the cathode 32 and is in close contact with the cathode 32 to supply negative current to the cathode 32 . The cathode water tank 37 is located outside the cathode power supply member 35 and is in close contact with the cathode power supply member 35 . The cathode main electrode 39 is positioned outside the cathode reservoir 37 and feeds a negative current to the cathode power supply member 35 .

In the electrolysis of water in the hydrogen gas generator 30, water (H ₂ O) is supplied to the anode water tank 36 and the cathode water tank 37 as indicated by arrows in FIG. A positive current is supplied, and a negative current is supplied to the cathode main electrode 39 from the power supply. The positive current fed to the anode main electrode 38 is fed from the anode feeding member 34 to the anode 31 (anode), and the negative current fed to the cathode main electrode 39 is fed from the cathode feeding member 35 to the cathode 32 (cathode). be done.

At the anode 31 (electrode 10A or electrode 10B), oxygen is generated by the anodic reaction (catalysis) of 2H ₂ O→4H ⁺ +4e ⁻ +O ₂ , and at the cathode 32 (electrode 10A or electrode 10B), 4H ⁺ +4e ⁻ → Hydrogen is produced by the cathodic reaction (catalysis) of _2H2 . Protons (hydrogen ions: H ⁺ ) move from the anode 31 to the cathode 32 through the solid polymer electrolyte membrane 33 . Protons generated at the anode 31 flow through the solid polymer electrolyte membrane 33 . at least three transition metals are selected from among the transition metals such that the composite work function of the work functions of the at least three transition metals approximates the work function of the platinum group element, and the selected at least three transition metals are The alloy powder 13 made from the Since the cathode 32 (the electrode 10A or the electrode 10B) is configured, the anode 31 and the cathode 32 exhibit excellent catalytic activity (catalytic action), electrolysis is efficiently performed in the hydrogen gas generator 30, and a large amount of hydrogen is produced in a short time. Hydrogen gas is generated.

The electrode 10A is an alloy obtained by pulverizing an alloy molding 42 which is fired after compressing a metal powder mixture 40 in which at least three types of transition metal powders selected from various transition metals are uniformly mixed and dispersed. Composite work function of work functions of at least three selected transition metals formed from powder 13 and carbon electrode plate 14 having a predetermined area carrying alloy powder 13 on both surfaces (front and rear surfaces 15 and 16) At least three types of transition metals are selected from among various transition metals so that the work function of the platinum group element is approximate to It has the same work function, can exhibit substantially the same catalytic activity (catalytic action) as an electrode containing a platinum group element, and can be suitably used as the electrode 10A of the fuel cell 21 and the hydrogen gas generator 30. .

Since the electrode 10A exhibits substantially the same catalytic activity (catalytic action) as an electrode containing a platinum group element, it is possible to generate sufficient electricity in the fuel cell 21 by using the electrode 10A in the fuel cell 21. can supply sufficient electrical energy to the load 29 connected to the fuel cell 21, and by using the electrode 10A in the hydrogen gas generator 30, electrolysis can be efficiently performed, and hydrogen A large amount of hydrogen gas can be generated in the gas generator 30 .

An electrode in which an alloy powder laminate porous structure 17 is formed on both surfaces (front and rear surfaces 15 and 16) of a carbon electrode plate 14 by a plurality of alloy powders 13 overlapping (laminated) in the thickness direction of the carbon electrode plate 14. 10B can increase the specific surface area of the alloy powder laminated porous structure 17 (alloy powder 13) by forming the alloy powder laminated porous structure 17 on both surfaces of the carbon electrode plate 14, and the alloy powder The catalytic action of the body 13 can be fully utilized, and the electrode 10B having the alloy powder laminated porous structure 17 has substantially the same work function as the electrode containing the platinum group element. Substantially the same catalytic activity (catalytic action) can be exhibited, and the electrode 10B of the fuel cell 21 and the hydrogen gas generator 30 can be suitably used.

Since the electrode 10B formed with the alloy powder laminated porous structure 17 exhibits substantially the same catalytic activity (catalytic action) as an electrode containing a platinum group element, the use of the electrode 10B in the fuel cell 21 , sufficient electricity can be generated in the fuel cell 21, sufficient electrical energy can be supplied to the load 29 connected to the fuel cell 21, and the electrode 10B can be used in the hydrogen gas generator 30. , the electrolysis can be efficiently performed, and a large amount of hydrogen gas can be generated in the hydrogen gas generator 30 . The electrode 10A and the electrode 10B are formed of at least three kinds of transition metals selected from various transition metals in the alloy powder 13 and the alloy powder laminated porous structure 17, and are made of platinum which does not use expensive platinum group elements. Therefore, the electrodes 10A and 10B can be manufactured at low cost.

The electrode 10A and the electrode 10B in which the metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) contains Ni (nickel) powder as a main component have the work function of Ni and other materials other than Ni. Powder of at least two transition metals other than Ni powder among various transition metals so that the composite work function of at least two transition metals approximates the work function of a platinum group element Since the material is selected, the electrodes 10A and 10B having the alloy powder 13 or the alloy powder laminated porous structure 17 have substantially the same work function as the electrode containing the platinum group element, and the electrode containing the platinum group element. Approximately the same catalytic activity (catalytic action) can be exhibited, and the electrodes 10A and 10B of the fuel cell 21 and the hydrogen gas generator 30 can be suitably used.

The electrode 10A and the electrode 10B in which the metal powder mixture 40 (the alloy powder 13 and the alloy powder laminated porous structure 17) is mainly composed of Ni (nickel) powder is substantially the same as the electrode containing a platinum group element. Since the electrode 10A and the electrode 10B are used in the fuel cell 21, sufficient electricity can be generated in the fuel cell 21, and the load 29 connected to the fuel cell 21 can generate electricity. Sufficient electrical energy can be supplied, and by using the electrodes 10A and 10B in the hydrogen gas generator 30, electrolysis can be efficiently performed, and a large amount of hydrogen gas can be generated in the hydrogen gas generator 30. can be generated. The electrodes 10A and 10B are composed of the alloy powder 13 or the alloy powder laminated porous structure 17 made of at least two kinds of transition metal powders other than Ni powder and Ni powder selected from various transition metals. The electrodes 10A and 10B can be manufactured at a low cost because they are platinum-less and do not use expensive platinum group elements.

The electrode 10A and the electrode 10B in which the metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) is mainly composed of Fe (iron) powder have the work function of Fe and other Powder of at least two other transition metals, excluding Fe powder, from among various transition metals such that the combined work function of at least two transition metals approximates the work function of a platinum group element Since the material is selected, the electrodes 10A and 10B having the alloy powder 13 or the alloy powder laminated porous structure 17 have substantially the same work function as the electrode containing the platinum group element, and the electrode containing the platinum group element. Approximately the same catalytic activity (catalytic action) can be exhibited, and the electrodes 10A and 10B of the fuel cell 21 and the hydrogen gas generator 30 can be suitably used.

The electrode 10A and the electrode 10B, in which the metal powder mixture 40 (the alloy powder 13 and the alloy powder laminated porous structure 17) is mainly composed of Fe (iron) powder, is substantially the same as the electrode containing a platinum group element. Since the electrode 10A and the electrode 10B are used in the fuel cell 21, sufficient electricity can be generated in the fuel cell 21, and the load 29 connected to the fuel cell 21 can generate electricity. Sufficient electrical energy can be supplied, and by using the electrodes 10A and 10B in the hydrogen gas generator 30, electrolysis can be efficiently performed, and a large amount of hydrogen gas can be generated in the hydrogen gas generator 30. can be generated. The electrode 10A and the electrode 10B are composed of the alloy powder 13 or the alloy powder laminated porous structure 17 made of Fe powder and at least two kinds of transition metal powder other than Fe powder selected from various transition metals. The electrodes 10A and 10B can be manufactured at a low cost because they are platinum-less and do not use expensive platinum group elements.

The metal powder mixture 40 (the alloy powder 13 and the alloy powder laminated porous structure 17) has Cu (copper) powder as the main component, and the electrode 10A and the electrode 10B have the work function of Cu and other materials other than Cu. Powders of at least two other transition metals, excluding Cu powder, from among various transition metals such that the composite work function with the work functions of at least two transition metals approximates the work function of a platinum group element Since the material is selected, the electrodes 10A and 10B having the alloy powder 13 or the alloy powder laminated porous structure 17 have substantially the same work function as the electrode containing the platinum group element, and the electrode containing the platinum group element. Approximately the same catalytic activity (catalytic action) can be exhibited, and the electrodes 10A and 10B of the fuel cell 21 and the hydrogen gas generator 30 can be suitably used.

The electrode 10A and the electrode 10B in which the metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) contains Cu (copper) powder as a main component are substantially the same as the electrode containing a platinum group element. Since the electrode 10A and the electrode 10B are used in the fuel cell 21, sufficient electricity can be generated in the fuel cell 21, and sufficient electricity can be supplied to the load connected to the fuel cell 21. In addition, by using the electrode 10A and the electrode 10B in the hydrogen gas generator 30, electrolysis can be performed efficiently, and a large amount of hydrogen gas is generated in the hydrogen gas generator 30. can be made The electrode 10A and the electrode 10B are composed of the alloy powder 13 or the alloy powder laminated porous structure 17 made of Cu powder and at least two kinds of transition metal powder other than Cu powder selected from various transition metals. The electrodes 10A and 10B can be manufactured at a low cost because they are platinum-less and do not use expensive platinum group elements.

12A and 12B are diagrams for explaining a method of manufacturing the electrodes 10A and 10B. As shown in FIG. 11, the electrodes 10A and 10B are produced in a transition metal selection step S1, a metal powder mixture preparation step S2, a metal powder compact preparation step S3, an alloy molding preparation step S4, and an alloy powder preparation step S5. , by an electrode manufacturing method having an alloy powder supporting step S6.

In the transition metal selection step S1, at least transition metals selected from various transition metals 41 are selected from at least three kinds of transition metals 41 so that the combined work function of the work functions of the transition metals 41 approximates the work function of the platinum group element. Three types of transition metals 41 (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 metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) containing Ni (nickel) as a main component, Cu (copper) and ZN (zinc) or Mn (manganese) and Mo (molybdenum). Ni (nickel) and Cu (copper) are selected in the metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) containing Fe (iron) as a main component, or Ti (titanium) and Ag (silver). In the metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) containing Cu (copper) as a main component, Fe (iron) and Zn (zinc) are selected, or Fe (iron) and Ag (silver).

In the metal powder mixture preparation step S2, a metal powder mixture 40 is prepared by uniformly mixing and dispersing powders 42 of at least three types of transition metals 41 selected in the transition metal selection step S1. In the metal powder mixture preparation step, in the metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) containing Ni (nickel) as a main component, Ni selected in the transition metal selection step S1, Cu (copper) and ZN (zinc) are each pulverized by a pulverizer to a particle size of 10 μm to 200 μm to prepare Ni powder 42 , Cu powder 42 and Zn powder 42 . Next, the Ni powder 42, the Cu powder 42, and the Zn powder 42 are put into a mixer, and the Ni powder 42, the Cu powder 42, and the Zn powder 42 are stirred and mixed by the mixer. By mixing, a metal powder mixture 40 in which Ni powder 42, Cu powder 42, and Zn powder 42 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 pulverized to a particle size of 10 μm to 200 μm by a pulverizer to obtain Ni powder 42, Mn A powder 42 of Mo and a powder 42 of Mo are prepared. Next, the Ni powder 42, the Mn powder 42, and the Mo powder 42 are put into a mixer, and the Ni powder 42, the Mn powder 42, and the Mo powder 42 are stirred and mixed by the mixer. By mixing, a metal powder mixture 40 in which Ni powder 42, Mn powder 42, and Mo powder 42 are uniformly mixed and dispersed is produced.

In the metal powder mixture preparation step S2, in the metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) containing Fe (iron) as a main component, Fe selected in the transition metal selection step S1 , Ni (nickel), and Cu (copper) are pulverized by a pulverizer to a particle size of 10 μm to 200 μm to prepare Fe powder 42 , Ni powder 42 , and Cu powder 42 . Next, the Fe powder 42, the Ni powder 42, and the Cu powder 42 are put into a mixer, and the Fe powder 42, the Ni powder 42, and the Cu powder 42 are stirred and mixed by the mixer. By mixing, a metal powder mixture 30 in which Fe powder 42, Ni powder 42, and Cu powder 42 are uniformly mixed and dispersed is produced.

Alternatively, each of Fe (iron), Ti (titanium), and Ag (silver) selected in the transition metal selection step S1 is pulverized to a particle size of 10 μm to 200 μm by a pulverizer to obtain Fe powder 42, Ti powder 42 and Ag powder 42 are prepared. Next, the Fe powder 42, the Ti powder 42, and the Ag powder 42 are put into a mixer, and the Fe powder 42, the Ti powder 42, and the Ag powder 42 are stirred and mixed by the mixer. By mixing, a metal powder mixture 40 in which Fe powder 42, Ti powder 42, and Ag powder 42 are uniformly mixed and dispersed is produced.

In the metal powder mixture preparation step S2, in the metal powder mixture 40 (alloy powder 13 and alloy powder laminated porous structure 17) containing Cu (copper) as a main component, Cu selected in the transition metal selection step S1 , Fe (iron), and Zn (zinc) are pulverized by a pulverizer to a particle size of 10 μm to 200 μm to prepare Cu powder 42 , Fe powder 42 , and Zn powder 42 . Next, the Cu powder 42, the Fe powder 42, and the Zn powder 42 are put into a mixer, and the Cu powder 42, the Fe powder 42, and the Zn powder 42 are stirred and mixed by the mixer. By mixing, a metal powder mixture 40 in which Cu powder 42, Fe powder 42, and Zn powder 42 are uniformly mixed and dispersed is produced.

Alternatively, each of Cu (copper), Fe (iron), and Ag (silver) selected in the transition metal selection step S1 is pulverized to a particle size of 10 μm to 200 μm by a pulverizer to obtain Cu powder 42, Fe powder 42 and Ag powder 42 are prepared. Next, the Cu powder 42, the Fe powder 42, and the Ag powder 42 are put into a mixer, and the Cu powder 42, the Fe powder 42, and the Ag powder 42 are stirred and mixed by the mixer. By mixing, a metal powder mixture 40 in which Cu powder 42, Fe powder 42, and Ag powder 42 are uniformly mixed and dispersed is produced.

In the metal powder compact creation step S3, the metal powder mixture 40 created in the metal powder mixture creation step S2 is pressed with a predetermined pressure to compress the metal powder mixture 40 into a metal powder having a predetermined area and a predetermined thickness. A compact 43 is made. In the metal powder compact production step S3, the metal powder mixture 40 is placed in a predetermined mold, and the metal powder compact 43 is produced by pressing the mold with a press machine. The press pressure (pressure) during press working is in the range of 500 Mpa to 800 Mpa.

If the pressing pressure (pressure) is less than 500 Mpa, the metal powder mixture 40 cannot be sufficiently compressed, and a metal powder compact 43 having a predetermined area and thickness cannot be produced. When the press pressure (pressure) exceeds 800 Mpa, the hardness of the alloy molded product 44 produced in the alloy molded product producing step S4 becomes unnecessarily high, and the alloy powder 13 having the desired particle size is produced in the alloy powder producing step S5. can't make In the electrode manufacturing method, by pressurizing (compressing) the metal powder mixture 40 with a pressure within the above range, a metal powder compact 43 having a predetermined hardness can be produced, and the metal powder compact 43 is fired. The alloy molding 44 having a predetermined hardness can be produced by pulverizing the alloy molding 44 to produce the alloy powder 13 having a predetermined particle size.

In the metal powder compact creation step S3, the metal powder compact 41 containing Ni (nickel) as a main component includes Ni powder 42, Cu (copper) powder 42, and ZN (zinc) powder 42. A predetermined amount of the mixed metal powder mixture 40 is put into a mold, and the metal powder mixture 40 is pressurized by press working to compress the metal powder mixture 40 to obtain a metal powder compact 43 having a predetermined area and a predetermined thickness. make. Alternatively, a predetermined amount of a metal powder mixture 40 in which Ni powder 42, Mn (manganese) powder 42, and Mo (molybdenum) powder 42 are mixed is put into a mold, and the metal powder mixture 40 is A metal powder compact 43 having a predetermined area and a predetermined thickness is produced by compressing the metal powder mixture 40 by press working.

In the metal powder compact creation step S3, the metal powder compact 41 containing Fe (iron) as a main component includes Fe powder 42, Ni (nickel) powder 42, and Cu (copper) powder 42. A predetermined amount of the metal powder mixture 40 mixed with make 43. Alternatively, a predetermined amount of a metal powder mixture 40 in which Fe powder 42, Ti (titanium) powder 42, and Ag (silver) powder 42 are mixed is put into a mold, and the metal powder mixture 40 is A metal powder compact 43 having a predetermined area and a predetermined thickness is produced by compressing the metal powder mixture 40 by press working.

In the metal powder compact creation step S3, the metal powder compact 41 containing Cu (copper) as a main component includes Cu powder 42, Fe (iron) powder 42, and Zn (zinc) powder 42. A predetermined amount of the metal powder mixture 40 mixed with the A powder compact 43 is made. Alternatively, a predetermined amount of a metal powder mixture 40 in which Cu powder 42, Fe (iron) powder 42, and Ag (silver) powder 42 are mixed is put into a mold, and the metal powder mixture 40 is A metal powder compact 43 having a predetermined area and a predetermined thickness is produced by compressing the metal powder mixture 40 by press working.

In the alloy molding production step S4, the metal powder compact 43 produced in the metal powder compact production step S3 is put into a furnace (steam heating furnace, electric furnace, etc.), and the metal powder compact 43 is placed in the furnace. By firing (sintering) at a predetermined temperature, an alloy molding 44 having a porous structure is produced in which a large number of fine flow paths (passage holes) with opening diameters in the range of 1 μm to 100 μm are formed. In the alloy molding production step S4, the metal powder compact 43 is fired for a long time at a temperature that melts at least two transition metals 41 out of the at least three transition metals 41 selected in the transition metal selection step S1. The firing (sintering) time is 3 to 6 hours. In the alloy molding production step S4, at the time of firing the metal powder compact 43 compressed to a predetermined area and thickness, the powder 42 of at least two types of transition metals 41 is melted, and the melted transition metals 41 are used as a binder. , the powder 42 of another transition metal 41 is joined (fixed).

In the alloy molding production step S4, in the metal powder compact 41 containing Ni (nickel) as a main component, Ni powder 42, Cu (copper) powder 42, and ZN (zinc) powder 42 are mixed. A metal powder compact 43 obtained by compressing a metal powder mixture 40 is sintered in a furnace for a long time to form a large number of fine flow paths (passage holes) with opening diameters in the range of 1 μm to 100 μm. make 44. In the alloy molding 44 formed from the Ni powder 42, the Cu powder 42, and the Zn powder 42, the metal powder is melted at a temperature (for example, 1100°C to 1200°C) at which the Zn and Cu powders 42 are melted. The compacted body 43 is fired (sintered), and the Ni powder 42 is joined (fixed) by the molten Zn and Cu powder 42 .

In addition, in the alloy molding production step S4, in the metal powder compact 43 containing Ni (nickel) as a main component, Ni powder 42, Mn (manganese) powder 42, and Mo (molybdenum) powder 42 A metal powder compact 43 obtained by compressing a metal powder mixture 40 mixed with An alloy molding 44 is made. In the alloy molding 44 formed from the Ni powder 42, the Mn powder 42, and the Mo powder 42, the metal powder is melted at a temperature (for example, 1460°C to 1500°C) at which the Mn and Ni powders 42 are melted. The compacted body 43 is sintered, and the Mo powder 42 is joined (fixed) by the molten Mn and Ni powder 42 .

In the alloy molding production step S4, in the metal powder compact 41 mainly composed of Fe (iron), Fe powder 42, Ni (nickel) powder 42, and Cu (copper) powder 42 are mixed. The metal powder compact 43 obtained by compressing the metal powder mixture 40 is sintered in a furnace for a long time to form a large number of fine flow paths (passage holes) with opening diameters in the range of 1 μm to 100 μm. Make thing 44. In the alloy molding 44 formed from the Fe powder 42, the Ni powder 42, and the Cu powder 42, the metal powder is melted at a temperature (for example, 1460° C. to 1500° C.) at which the Cu and Ni powders 42 are melted. The Fe powder 42 is joined (fixed) by the Cu and Ni powder 42 melted by sintering the body compact 43 .

In addition, in the alloy molding production step S4, in the metal powder compact 41 containing Fe (iron) as a main component, Fe powder 42, Ti (titanium) powder 42, and Ag (silver) powder 42 A metal powder compact 43 obtained by compressing a metal powder mixture 40 mixed with An alloy molding 44 is made. In the alloy molding 44 formed from the Fe powder 42, the Ti powder 42, and the Ag powder 42, the metal powder is melted at a temperature (for example, 1540° C. to 1600° C.) at which the Ag and Fe powder 42 is melted. The compacted body 43 is sintered, and the Ti powder 42 is joined (fixed) by the molten Ag and Fe powder 42 .

In the alloy molding production step S4, in the metal powder compact 41 mainly composed of Cu (copper), Cu powder 42, Fe (iron) powder 42, and Zn (zinc) powder 42 are mixed. The metal powder compact 43 obtained by compressing the metal powder mixture 40 is sintered in a furnace for a long time to form a large number of fine flow paths (passage holes) with opening diameters in the range of 1 μm to 100 μm. Make thing 44. In the alloy molding 44 formed from the Cu powder 42, the Fe powder 42, and the Zn powder 42, the metal powder is melted at a temperature (for example, 1090°C to 1200°C) at which the Zn and Cu powders 42 are melted. The compacted body 43 is sintered, and the Fe powder 42 is joined (fixed) by the molten Zn and Cu powder 42 .

In addition, in the alloy molding production step S4, the metal powder compact 41 containing Cu (copper) as a main component includes Cu powder 42, Fe (iron) powder 42, and Ag (silver) powder 42. A metal powder compact 43 obtained by compressing a metal powder mixture 40 mixed with An alloy molding 44 is made. In the alloy molding 44 formed from the Cu powder 42, the Fe powder 42, and the Ag powder 42, the metal powder is melted at a temperature (for example, 1090°C to 1200°C) at which the Ag and Cu powders 42 are melted. The body compact 43 is fired, and the Fe powder 42 is joined (fixed) by the molten Ag and Cu powder 42 .

In the alloy powder production step S5, the alloy powder 13 is produced by pulverizing the alloy molded product 44 produced in the alloy molded product production step S4 to a particle size of 10 μm to 200 μm using a pulverizer. As an example of the alloy powder 13 containing Ni (nickel) as a main component (alloy powder containing Ni as a main component), Ni powder 42, Cu powder 42, and ZN powder 42 are uniformly mixed.・The metal powder compact 43 obtained by compressing the dispersed metal powder mixture 40 is sintered to make an alloy molding 44, and the alloy molding 44 is finely pulverized to a particle size of 10 μm to 200 μm by a pulverizer. It is a thing. Another example of the alloy powder 13 containing Ni (nickel) as a main component is a metal powder mixture 40 in which Ni powder 42, Mn powder 42, and Mo powder 42 are uniformly mixed and dispersed. The compacted metal powder 43 is sintered to form an alloy molding 44, and the alloy molding 44 is pulverized to a particle size of 10 μm to 200 μm by a pulverizer.

As an example of the alloy powder 13 containing Fe (iron) as a main component (an alloy powder containing Fe as a main component), Fe powder 42, Ni powder 42, and Cu powder 42 are uniformly mixed.・The metal powder compact 43 obtained by compressing the dispersed metal powder mixture 40 is sintered to make an alloy molding 44, and the alloy molding 44 is finely pulverized to a particle size of 10 μm to 200 μm by a pulverizer. It is a thing. Another example of the alloy powder 13 containing Fe (iron) as a main component is a metal powder mixture 40 in which Fe powder 42, Ti powder 42, and Ag powder 42 are uniformly mixed and dispersed. The compacted metal powder 43 is sintered to form an alloy molding 44, and the alloy molding 44 is pulverized to a particle size of 10 μm to 200 μm by a pulverizer.

As an example of the alloy powder 13 containing Cu (copper) as a main component (an alloy powder containing Cu as a main component), Cu powder 42, Fe powder 42, and Zn powder 42 are uniformly mixed.・The metal powder compact 43 obtained by compressing the dispersed metal powder mixture 40 is sintered to make an alloy molding 44, and the alloy molding 44 is finely pulverized to a particle size of 10 μm to 200 μm by a pulverizer. It is a thing. Another example of the alloy powder 13 containing Cu (copper) as a main component is a metal powder mixture 40 in which Cu powder 42, Fe powder 42, and Ag powder 42 are uniformly mixed and dispersed. The compacted metal powder 43 is sintered to form an alloy molding 44, and the alloy molding 44 is pulverized to a particle size of 10 μm to 200 μm by a pulverizer.

In the alloy powder supporting step S6, the plurality of alloy powders 13 produced in the alloy powder producing step S5 are placed on the entire front surface 15 of the carbon electrode plate 14 having a predetermined area and a thickness L1 of 0.03 mm to 0.3 mm. It is carried on the entire area of the rear surface 16 (the entire area on both sides). In addition, in the alloy powder supporting step S6, a plurality of alloy powders 13 are overlapped (stacked) in the thickness direction of the carbon electrode plate 14, and the alloy powders 13 are spread over a predetermined area and 0.03 mm to 0.05 mm. The carbon electrode plate 14 having a thickness L1 of 3 mm is supported on the entire front surface 15 and the rear surface 16 (both surfaces) of the carbon electrode plate 14, and the alloy powder 13 overlaps (stacks) in the thickness direction of the carbon electrode plate 14. The alloy powder laminate porous structure 17 described above is formed. In the alloy powder supporting step S6, the alloy powder 13 is supported on both surfaces of the carbon electrode plate 14 by a conductive binder (conductive binding material) or plasma spraying.

In the electrode manufacturing method, at least three of various transition metals 41 are selected from various transition metals 41 so that the combined work function of the work functions of at least three transition metals 41 approximates the work function of the platinum group element. a transition metal selection step S1 for selecting a type of transition metal 41; a powder mixture preparation step S2; a metal powder compact preparation step S3 in which the metal powder mixture 40 prepared in the metal powder mixture preparation step S2 is pressurized with a predetermined pressure to prepare a metal powder compact 43; An alloy compact creation step S4 in which the metal powder compact 43 created in the powder compact creation step S3 is fired at a predetermined temperature to create an alloy compact 44, and an alloy compact created in the alloy compact creation step S4. An alloy powder preparation step S5 in which the material 44 is finely pulverized to prepare the alloy powder 13, and the alloy powder 13 prepared in the alloy powder preparation step S5 is applied to both surfaces of the carbon electrode plate 14 having a predetermined area (front and rear surfaces 15, 16) Since the electrode 10A or the electrode 10B is manufactured by each step of the alloy powder supporting step S6 to be supported in the step S6, the platinum-less electrodes 10A and 10B that do not use a platinum group element can be manufactured at a low cost, and the catalyst function is improved. It is possible to make electrodes 10A and 10B that can be used sufficiently and reliably, have excellent catalytic activity (catalytic action), and can be suitably used in the fuel cell 21 and the hydrogen gas generator 30. can.

In the electrode manufacturing method, the alloy powder 13 is supported on the entire front surface 15 and the rear surface 16 of the carbon electrode plate 14 having a thickness L1 in the range of 0.03 mm to 0.3 mm. or the electrode 10B formed with the alloy powder laminated porous structure 17 in which a plurality of alloy powders 13 are overlapped, the electrical resistance of the electrodes 10A and 10B can be lowered, and the electrode The electrodes 10A, 10A, 10A, 10A, 10B, 10A, 10B, 10A, 10B, 10A, 10B, 10A, 10B, 10A, 10B, 10A, 10B, 10A, 10B, and 10B are provided. The electrode 10A and the electrode 10B are capable of producing the electrode 10B, efficiently performing electrolysis in the hydrogen gas generator 30, and generating a large amount of hydrogen gas in a short time in the hydrogen gas generator 30. can be made.

10A electrode 10B electrode 11 front surface 12 rear surface 13 alloy powder (alloy powder)
14 Carbon electrode plate 15 Front surface 16 Rear surface 17 Alloy powder laminated porous structure 18 Flow path 19 Flow port 20 Cell 21 Fuel cell 22 Fuel electrode 23 Air electrode 24 Solid polymer electrolyte membrane (fluorinated ion exchange having sulfonic acid group film)
25a separator (bipolar plate)
25b separator (bipolar plate)
26a Gas diffusion layer 26b Gas diffusion layer 27a Gas seal 27b Gas seal 28 Wire 29 Load 30 Hydrogen gas generator 31 Anode 32 Cathode 33 Solid polymer electrolyte membrane (fluorinated ion exchange membrane having sulfonic acid groups)
34 Anode feeding member 35 Cathode feeding member 36 Anode water tank 37 Cathode water tank 38 Anode main electrode 39 Cathode main electrode 40 Metal powder mixture 41 Transition metal 42 Powder 43 Metal powder compact 44 Alloy molding (alloy molding Stuff)

Claims (15)

In the electrodes used as anodes or cathodes,
an alloy powder obtained by pulverizing an alloy molding obtained by compressing a metal powder mixture in which at least three kinds of transition metal powders selected from various transition metals are uniformly mixed and dispersed and then firing the electrode, and a carbon electrode plate having a predetermined area on both sides of which the alloy powder is supported. In the metal powder mixture, the composite work function of the work functions of the selected at least three transition metals is An electrode in which at least three transition metals are selected from the various transition metals so as to approximate the work function, wherein a composite work function of the work functions of the three transition metals is 48Ni-42Cu -10Zn, 48Ni-45Mo-7Mn, 48Fe-48Ni-4Cu, 48Fe-46Ti-6Ag, 48Cu-48Fe-4Zn, or at least the work function of the alloy powder having a composition (weight ratio) of 48Cu-46Fe-6Ag An electrode characterized by: 2. The electrode according to claim 1, wherein an alloy powder laminate porous structure is formed by said alloy powder overlapping in the thickness direction of said carbon electrode plate on both surfaces of said carbon electrode plate. The particle size of the transition metal powder is in the range of 10 μm to 200 μm, the particle size of the alloy powder is in the range of 10 μm to 200 μm, and the thickness dimension of the carbon electrode plate is 0.03 mm to 0.03 mm. 3. An electrode according to claim 1 or claim 2 in the range of 0.3 mm. The metal powder mixture contains Ni (nickel) powder as a main component, and in the metal powder mixture, the work function of Ni and the work functions of at least two transition metals other than Ni are synthesized. 2. At least two types of transition metal powder other than the Ni powder are selected from the various transition metals so that the work function approximates the work function of the platinum group element. The electrode according to any one of claims 1 to 3. The weight ratio of the Ni (nickel) 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 The weight ratio to the total weight of the powder mixture is in the range of 20% to 50%, and the weight of at least one transition metal powder other than the Ni powder to the total weight of the metal powder mixture Electrode according to claim 4, wherein the ratio is in the range of 3% to 20%. The metal powder mixture contains Fe (iron) powder as a main component, and in the metal powder mixture, the work function of Fe and the work functions of at least two other transition metals other than Fe are synthesized. 2. At least two transition metal powders other than the Fe powder are selected from among the various transition metals so that the work function approximates the work function of the platinum group element. The electrode according to any one of claims 1 to 3. The weight ratio of the Fe (iron) 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 The weight ratio to the total weight of the powder mixture is in the range of 20% to 50%, and the weight of at least one transition metal powder other than the Fe powder to the total weight of the metal powder mixture 7. Electrode according to claim 6, wherein the ratio is in the range of 3% to 20%. The metal powder mixture contains Cu (copper) powder as a main component, and in the metal powder mixture, the work function of Cu and the work functions of at least two transition metals other than Cu are synthesized. 2. At least two transition metal powders other than the Cu powder are selected from the various transition metals so that the work function approximates the work function of the platinum group element. The electrode according to any one of claims 1 to 3. The weight ratio of the Cu (copper) 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 The weight ratio to the total weight of the powder mixture is in the range of 20% to 50%, and the weight of at least one transition metal powder other than the Cu powder to the total weight of the metal powder mixture Electrode according to claim 8, wherein the ratio is in the range of 3% to 20%. In the alloy molded product, at least two transition metals among the selected transition metals are melted during firing of the metal powder mixture, and the transition metal powders are bonded using the melted transition metals as a binder. 10. The electrode according to any one of claims 1-9. In an electrode manufacturing method for manufacturing an electrode used as an anode or a cathode,
At least three transition metals selected from the various transition metals are used so that the combined work function of the work functions of at least three transition metals selected from the various transition metals approximates the work function of the platinum group element. and a metal powder mixture preparation step of preparing a metal powder mixture by uniformly mixing and dispersing powders of at least three types of transition metals selected in the transition metal selection step. a metal powder compact creation step of pressurizing the metal powder mixture created in the metal powder mixture creation step at a predetermined pressure to make a metal powder compact; an alloy molded article producing step for producing an alloy molded article by sintering the compressed metal powder at a predetermined temperature; and an alloy powder carrying step of carrying the alloy powder produced in the alloy powder producing step on both sides of a carbon electrode plate having a predetermined area, wherein the three kinds of transitions The composite work function of the metal work function is 48Ni-42Cu-10Zn, 48Ni-45Mo-7Mn, 48Fe-48Ni-4Cu, 48Fe-46Ti-6Ag, 48Cu-48Fe-4Zn, or a composition of 48Cu-46Fe-6Ag ( weight ratio) is equal to or higher than the work function of the alloy powder .


The metal powder mixture producing step pulverizes the at least three transition metals selected in the transition metal selecting step to a particle size of 10 μm to 200 μm, and the alloy powder producing step pulverizes the alloy molded product to a particle size of 10 μm. 12. The method of manufacturing an electrode according to claim 11, wherein the powder is pulverized to a particle size of ~200 μm. Claim 11 or Claim 12, wherein the metal powder compact creation step presses the metal powder mixture created by the metal powder mixture creation step with a pressure of 500 Mpa to 800 Mpa to create the metal powder compact. The electrode manufacturing method according to . In the step of preparing an alloy molded product, the metal powder compact is fired at a temperature at which at least two transition metals selected in the transition metal selection step are melted, and the melted transition metal is used as a binder. 14. The electrode manufacturing method according to any one of claims 11 to 13, wherein the transition metal powders are bonded. In the alloy powder carrying step, the alloy powder is carried on both sides of the carbon electrode plate having a thickness of 0.03 mm to 0.3 mm, and the carbon is supported by the alloy powder overlapping in the thickness direction of the carbon electrode plate. 15. The method for manufacturing an electrode according to any one of claims 11 to 14, wherein the alloy powder laminate porous structure is formed on both sides of the electrode plate.

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