JP2020084291A - Electrolyzer - Google Patents

Abstract

To provide an electrolyzer provided with an anode and a cathode having excellent catalytic activity regardless of a low platinum group metal content, capable of efficiently performing electrolysis by using the anode and the cathode, and generating a large amount of hydrogen gas in a short time.SOLUTION: An anode 11 and a cathode 12 forming an electrolyzer 10 are formed of at least one kind of a small amount of platinum group metal selected from various platinum group metals and at least two kinds of transition metals selected from various transition metals. A prescribed pore formation material is added to a metal fine powder mixture obtained by uniformly mixing and dispersing platinum group metal fine powders obtained by finely pulverizing the selected at least one kind of platinum group metal and transition metal fine powders obtained by pulverizing the selected at least two kinds of transition metals, and a prescribed binder, the metal fine powder mixture added with the pore formation material is molded into a sheet shape with a prescribed area, and the metal fine powder molding molded into the sheet shape with the prescribed area is degreased and sintered so as to be sheet-shaped electrodes with a microporous structure formed with many fine pores.SELECTED DRAWING: Figure 1

Description

The present invention relates to an electrolyzer that chemically decomposes a predetermined aqueous solution using electricity.

A reaction tube, a catalyst body housed in the reaction tube, and a tubular body having a fluid inlet and a fluid outlet, wherein the fluid inlet and the fluid outlet communicate with each other using the interior of the tubular body as a flow path. Is disposed in the flow channel, the catalyst body is inserted into the reaction tube in a direction in which the axis is parallel to the longitudinal direction of the reaction tube, and the catalyst body includes a base material extending along a certain axis and a dehydrogenation catalyst. A dehydrogenation catalyst layer, the base material includes a plate-shaped portion extending along the axis while twisting in a direction of rotation about the axis, and the dehydrogenation catalyst layer is provided on the surface of the plate-shaped portion. A hydrogen generator is disclosed (see Patent Document 1).

JP, 2016-55251, A

The catalyst body of the hydrogen generator disclosed in Patent Document 1 includes a step of forming a metal oxide film containing a metal oxide by anodizing the surface of a metal molded body, and a dehydrogenation catalyst on the metal oxide film. And the step of supporting. In the step of supporting the dehydrogenation catalyst on the metal oxide film, hexachloroplatinate (IV) acid ions are added to the metal oxide film by bringing an acidic platinum chloride aqueous solution containing hexachloroplatinate (IV) ion into contact with the metal oxide film. And the metal oxide film to which hexachloroplatinate (IV) acid ions are attached is baked to support platinum as a dehydrogenation catalyst on the metal oxide film.

Various platinum-supporting carbons are widely used as the anode and cathode of the electrolyzer. However, since platinum is a precious metal and a rare resource with a limited production amount, it is required to suppress its use. Further, in order to popularize electrolysis devices in the future, it is required to reduce the content of expensive platinum as much as possible and to develop an anode and a cathode using a metal other than platinum together with a small amount of platinum.

An object of the present invention is to provide a positive electrode and a negative electrode having excellent catalytic activity (catalytic action) even though the platinum group metal content can be minimized and the platinum group metal content is low. An object of the present invention is to provide an electrolyzer which can efficiently perform electrolysis using an anode and a cathode and can generate a large amount of hydrogen gas in a short time.

The electrolyzer of the present invention for solving the above-mentioned problems includes an anode and a cathode, and an electrode assembly film that is located between the anode and the cathode and joins the electrodes, and the anode and the cathode are various. The anode and the cathode are made of at least one small amount of platinum group metal selected from the platinum group metals and at least two kinds of transition metals selected from various transition metals, and the anode and the cathode are made of at least one selected platinum group. Formation of predetermined pores in a fine metal powder mixture in which a platinum group metal fine powder obtained by finely pulverizing a group metal and a transition metal fine powder obtained by finely pulverizing at least two selected transition metals and a predetermined binder are uniformly mixed and dispersed Material is added and the fine pore metal mixture is added to form a thin plate with a predetermined area, and the fine metal powder formed into a thin plate with a predetermined area is degreased and sintered to produce a large number of fine particles. It is a thin plate electrode of microporous structure with various pores, and electricity is applied to the thin plate shaped anode and cathode of microporous structure, by causing an oxidation reaction at the anode and a reduction reaction at the cathode. It is characterized by chemically decomposing a predetermined aqueous solution.

As an example of the electrolyzer of the present invention, in the anode and the cathode, various transition metals are selected so that the composite work function of the work functions of at least two selected transition metals approximates to the work function of the platinum group metal. At least two kinds of transition metals are selected from among them.

As another example of the electrolyzer of the present invention, the average diameter of the pores formed in the anode and the cathode is in the range of 1 to 100 μm.

As another example of the electrolyzer of the present invention, the thickness dimension of the anode and the thickness dimension of the cathode are in the range of 0.03 mm to 1.5 mm.

As another example of the electrolyzer of the present invention, the platinum group metal is Pt (platinum), the transition metals are Ni (nickel) and Fe (iron), and the work of Ni in the anode and the cathode. Ratio of the Pt platinum group metal fine powder to the total weight of the metal fine powder mixture and the Ni transition metal fine powder so that the composite work function of the function and the work function of Fe approximates the work function of the platinum group metal. A weight ratio to the total weight of the metal fine powder mixture and a weight ratio of Fe transition metal fine powder to the total weight of the metal fine powder mixture are defined.

As another example of the electrolyzer of the present invention, the weight ratio of the platinum group metal fine powder of Pt to the total weight of the metal fine powder mixture is in the range of 4 to 10%, and the metal fine powder of the transition metal fine powder of Ni is The weight ratio to the total weight of the mixture is in the range of 45% to 48%, and the weight ratio of the transition metal fine powder of Fe to the total weight of the metal fine powder mixture is in the range of 45% to 48%.

As another example of the electrolyzer of the present invention, the porosity of the thin plate-shaped anode and cathode having a microporous structure is in the range of 70% to 85%.

As another example of the electrolytic apparatus of the present invention, the anode and the density of the cathode which is formed into a thin microporous structure ^is in the range of ^{6.0g / cm 2 ~8.0g / cm 2} .

As another example of the electrolyzer of the present invention, the particle size of the platinum group metal fine powder of the platinum group metal and the particle size of the transition metal fine powder of the transition metal are in the range of 1 μm to 100 μm.

According to the electrolyzer according to the present invention, the anode and the cathode used therein are at least one small amount of platinum group metal selected from various platinum group metals and at least two types selected from various transition metals. Formed from a transition metal of
A metal in which a platinum group metal fine powder obtained by finely pulverizing at least one selected platinum group metal and a transition metal fine powder obtained by finely pulverizing at least two selected transition metals and a predetermined binder are uniformly mixed and dispersed. A predetermined pore-forming material is added to the fine powder mixture, the metal fine-powder mixture containing the pore-forming material is molded into a thin plate with a predetermined area, and the metal fine powder molded product with a thin plate with a predetermined area is degreased and baked. By binding, since it is a thin plate electrode having a microporous structure in which a large number of fine pores are formed, by using a transition metal other than the platinum group metal, the content of the platinum group metal can be minimized as much as possible. In addition, it is possible to efficiently perform electrolysis using the anode and the cathode that utilize the catalytic activity of the platinum group metal and the catalytic activity of the transition metal, and to generate a large amount of hydrogen gas in a short time. it can.

At least two kinds of transition metals are selected from among various kinds of transition metals so that the composite work functions of the work functions of the selected at least two kinds of transition metals are close to the work functions of the platinum group metal in the anode and the cathode. In the electrolyzer, at least two kinds of transition metals are selected from among various kinds of transition metals so that the synthetic work function approximates the work function of platinum group metals, and thus the content of platinum group metals is small. Nevertheless, the anode and the cathode have substantially the same work function as the platinum-supported electrode, and the anode and the cathode exhibit substantially the same catalytic activity (catalytic action) as the platinum-supported electrode, and at least the selected Electrolysis can be efficiently carried out using an anode and a cathode containing two kinds of transition metals and having excellent catalytic activity, and a large amount of hydrogen gas can be generated in a short time.

Since the electrolysis apparatus in which the average diameter of the pores formed in the anode and the cathode is in the range of 1 to 100 μm, the average diameter of the pores formed in the anode and the cathode is in the range of 1 to 100 μm. A large number of pores are formed per volume, the specific surface area of the anode and the cathode can be increased, and the liquid can be brought into wide contact with the contact surfaces of the anode and the cathode by allowing the liquid to flow through the pores. The catalysis of the anode and the cathode can be fully utilized. The electrolyzer can efficiently perform electrolysis by using an anode and a cathode having an average diameter in the range of 1 to 100 μm and having excellent catalytic activity, and generate a large amount of hydrogen gas in a short time. Can be made

The electrolysis device in which the thickness dimension of the anode and the thickness dimension of the cathode are in the range of 0.03 mm to 1.5 mm reduces the electrical resistance of the anode and the cathode by setting the thickness dimension of the anode and the cathode in the above range. Therefore, the current can be smoothly passed through the anode and the cathode. The electrolyzer has an anode and a cathode having substantially the same catalytic activity (catalyst action) as an electrode supporting a platinum group metal, and the electric resistance of the anode and the cathode is small, and a current flows smoothly through the anode and the cathode. Electrolysis can be efficiently performed using an anode and a cathode having excellent catalytic activity and low potential resistance, and a large amount of hydrogen gas can be generated in a short time.

The platinum group metal is Pt (platinum), the transition metals are Ni (nickel) and Fe (iron), and the combined work function of the work function of Ni and the work function of Fe is close to the work function of the platinum group metal. Thus, the weight ratio of Pt platinum group metal fine powder to the total weight of the metal fine powder mixture and the weight ratio of Ni transition metal fine powder to the total weight of the metal fine powder mixture and Fe transition metal fine powder to the metal fine powder The electrolysis apparatus, in which the weight ratio to the total weight of the body mixture is defined, is such that the composite work function of the transition metal approximates the work function of the platinum group metal, and the platinum group of Pt relative to the total weight of the fine metal powder mixture. Since the weight ratio of the metal fine powder, the weight ratio of the transition metal fine powder of Ni to the total weight of the metal fine powder mixture, and the weight ratio of the transition metal fine powder of Fe to the total weight of the metal fine powder mixture are determined, The cathode and the cathode have almost the same work function as the platinum-supported electrode, the anode and the cathode have excellent catalytic activity (catalysis), and the anode and the cathode have the same catalytic activity (catalyst) as the platinum-supported electrode. By exhibiting the action), electrolysis can be efficiently performed using the anode and the cathode, and a large amount of hydrogen gas can be generated in a short time. In the electrolyzer, since the anode and the cathode contain Ni (nickel) and Fe (iron) and the content of Pt (platinum) is small, the material cost of the anode and the cathode can be reduced. It can be manufactured at low cost and the operating cost of the electrolyzer can be reduced.

The weight ratio of Pt platinum group metal fine powder to the total weight of the metal fine powder mixture is in the range of 4 to 10%, and the weight ratio of Ni transition metal fine powder to the total weight of the metal fine powder mixture is 45% to 48%. Range, the electrolysis device having a weight ratio of the transition metal fine powder of Fe to the total weight of the fine metal powder mixture in the range of 45% to 48% has a synthetic work function of Ni (nickel) close to that of a platinum group metal. ) And Fe (iron), the weight ratio of the platinum group metal fine powder of Pt to the total weight of the metal fine powder mixture, the weight ratio of the transition metal fine powder of Ni to the total weight of the metal fine powder mixture, and the metal By setting the weight ratio of the Fe transition metal fine powder to the total weight of the fine powder mixture within the above range, the synthetic work function of the work functions of the Ni transition metal fine powder and the Fe transition metal fine powder can be calculated as follows. A catalyst that can be approximated to a work function and has excellent catalytic activity (catalysis) in the anode and the cathode even though the Pt content is small, and the anode and the cathode are substantially the same as the platinum-supported electrode. By exhibiting the activity (catalytic action), electrolysis can be efficiently performed using the anode and the cathode, and a large amount of hydrogen gas can be generated in a short time. In the electrolyzer, the anode and the cathode include Ni (nickel) and Fe (iron) in the weight ratios described above, the weight ratio of Pt (platinum) to the total weight of the fine metal powder mixture is small, and Pt (platinum) is contained. Since the amount is small, the material cost of the anode and the cathode can be reduced, the electrolyzer can be manufactured at low cost, and the operating cost of the electrolyzer can be reduced.

The electrolyzer in which the porosity of the anode and cathode formed in the shape of a microporous thin plate is in the range of 70% to 85%, a large number of anodes and cathodes can be obtained by adjusting the porosities of the anode and cathode to the above range. Is formed into a porous structure having fine pores (passage holes) (microporous structure having an average diameter of pores of 1 to 100 μm), the specific surface area of the anode and the cathode can be increased, and liquid flows through these pores. It is possible to bring the liquid into contact with the contact surfaces of the pores of the anode and cathode over a wide range, and the anode and cathode reliably exhibit the same catalytic activity (catalytic action) as the platinum-supported electrode, ensuring a sufficient catalytic function. In addition, it is possible to efficiently use the anode and the cathode, which can be reliably used and have excellent catalytic activity (catalyst action), to efficiently perform electrolysis, and to generate a large amount of hydrogen gas in a short time. it can.

Micro density of the shaped anode and cathode sheet of the porous structure electrolyzer in the range of 6.0g ^/ cm ² ~8.0g / cm 2, by making the density of the anode and cathode to said range, The anode and the cathode are molded into a porous structure having a large number of fine pores (passage holes) (microporous structure having an average diameter of the pores of 1 to 100 μm), and the specific surface area of the anode and the cathode can be increased. It is possible to bring the liquid into wide contact with the contact surfaces of the pores of the anode and cathode while the liquid is flowing, and the anode and cathode reliably exhibit the same catalytic activity (catalytic action) as the electrode supporting platinum. , The catalytic function can be used sufficiently and reliably, and the electrolysis can be efficiently performed using the anode and the cathode having excellent catalytic activity (catalytic action), and a large amount of hydrogen gas can be obtained in a short time. Can be generated.

An electrolysis apparatus in which the particle size of the platinum group metal fine powder of the platinum group metal and the particle size of the transition metal fine powder of the transition metal are in the range of 1 μm to 100 μm is used for the electrolysis device of the platinum group metal of the platinum group metal and the transition metal. By setting the particle size of the transition metal fine powder within the above range, the anode and the cathode are formed into a porous structure having a large number of fine pores (passage holes) (microporous structure having an average pore diameter of 1 to 100 μm), And, the specific surface area of the cathode can be increased, and it becomes possible to bring the liquid into wide contact with the contact surface of the pores of the anode and the cathode while the liquid flows through the pores, and the anode or the cathode carries platinum. Electrolysis using an anode and a cathode that can exhibit catalytic activity (catalyst action) almost the same as above, and can fully and surely utilize the catalytic function and has excellent catalytic activity (catalyst action). Can be efficiently performed, and a large amount of hydrogen gas can be generated in a short time.

The side view of the electrolysis apparatus shown as an example. The perspective view of the anode and the cathode shown as an example. The elements on larger scale shown as an example of an anode and a cathode. The figure explaining an example of electrolysis using an electrolyzer. The figure which shows an example of the hydrogen gas generation system using an electrolyzer. FIG. 3 is a side view of a polymer electrolyte fuel cell using an air electrode (anode) and a fuel electrode (cathode). The figure which shows the result of the electromotive voltage test of an anode and a cathode. The figure which shows the result of the IV characteristic test of an anode and a cathode. 6A to 6C are views illustrating a method of manufacturing an anode and a cathode.

With reference to the accompanying drawings such as FIG. 1 which is a side view of the electrolysis apparatus 10 shown as an example, the details of the electrolysis apparatus according to the present invention and a method for manufacturing an anode and a cathode used in the electrolysis apparatus will be described below. It is as follows. 2 is a perspective view of the anode 11 and the cathode 12 shown as an example, and FIG. 3 is a partially enlarged view showing the anode 11 and the cathode 12 as an example. In FIG. 2, the thickness direction is indicated by arrow X, and the radial direction is indicated by arrow Y.

The electrolyzer 10 (hydrogen gas generator) includes an anode 11 (anode), a cathode 12 (cathode), and a solid polymer electrolyte membrane 13 (electrode assembly membrane) located (interposed) between the anode 11 and the cathode 12. ) (Fluorine-based ion exchange membrane having sulfonic acid group), anode power supply member 14 and cathode power supply member 15, anode water storage tank 16 and cathode water storage tank 17, anode main electrode 18 and cathode main electrode 19 Has been formed.

The electrolyzer 10 energizes the anode 11 and the cathode 12 to cause an oxidation reaction at the anode 11 and a reduction reaction at the cathode 12, thereby chemically decomposing a predetermined aqueous solution. In the electrolyzer 10, the anode 11 and the cathode 12 and the solid polymer electrolyte membrane 13 are integrated in the thickness direction by overlapping and forming a membrane/electrode assembly 20 (Membrane Electrode Assembly, MEA). Is sandwiched between the anode power feeding member 14 and the cathode power feeding member 15. In the membrane/electrode assembly 20, the surface of the anode 11 is closely attached to one surface of the solid polymer electrolyte membrane 13 by hot pressing and the surface of the cathode 12 is closely attached to the other surface of the solid polymer electrolyte membrane 13 by hot pressing. It is in close contact. The solid polymer electrolyte membrane 13 has proton conductivity and no electron conductivity.

The anode power supply member 14 is located outside the anode 11 and is in close contact with the anode 11, and supplies a positive current to the anode 11. The anode water storage tank 16 is located outside the anode power feeding member 14 and is in close contact with the anode power feeding member 14. The anode main electrode 18 is located outside the anode water storage tank 16 and supplies a positive current to the anode power supply member 14. The cathode power supply member 15 is located outside the cathode 12 and is in close contact with the cathode 12, and supplies a negative current to the cathode 12. The cathode water storage tank 17 is located outside the cathode power supply member 15 and is in close contact with the cathode power supply member 15. The cathode main electrode 19 is located outside the cathode water storage tank 17 and supplies negative current to the cathode power supply member 15.

The anode 11 and the cathode 12 used in the electrolyzer 10 (hydrogen gas generator) have a front surface 21 and a rear surface 22, have a predetermined area and a predetermined thickness dimension L1, and have a planar shape formed into a quadrangle. ing. The anode 11 and the cathode 12 are porous (microporous structure) thin plate electrodes 24 (foamed metal electrodes) having a large number of fine pores 23 (continuous and independent passage holes). An aqueous solution (liquid) flows through the pores 23. The planar shapes of the anode 11 and the cathode 12 are not particularly limited, and in addition to the quadrangle, any other planar shape such as a circle or an ellipse can be formed according to the application.

The anode 11 and the cathode 12 are formed of a powder-processed platinum group metal 49 and at least two kinds of transition metals 50 selected from powder-processed transition metals 50. As the platinum group metal 49, platinum (Pt), palladium (Pb), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium (Os) can be used. For the platinum group metal 49, at least one of them is used. As the transition metal 50, 3d transition metal or 4d transition metal is used. Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), and Zn (zinc) are used as the 3d transition metal. Nb (niobium), Mo (molybdenum), and Ag (silver) are used as the 4d transition metal. At least two of them are used for the transition metal 50.

In the anode 11 and the cathode 12, transitions are made so that the composite work function of the work functions (energy required to extract electrons from the substance) of at least two kinds of selected transition metals 50 approximates the work function of the platinum group metal. At least two kinds of transition metals 50 are selected from the metals 50. The work function of platinum is 5.65 (eV). 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) and Nb have work functions of 4.01 (eV), Mo has a work function of 4.45 (eV), and Ag has a work function of 4.31 (eV).

The anode 11 and the cathode 12 are platinum group metal fine powder of platinum group metal 49 (Pt (platinum) processed into fine powder, Pb (palladium) processed into fine powder, Rh (rhodium) processed into fine powder). , Finely powdered Ru (ruthenium), finely powdered Ir (iridium), finely powdered Os (osmium)), and at least two kinds of those selected from various transition metals 50 Transition metal fine powder of transition metal 50 (Ti (titanium) processed into a fine powder, Cr (chrome) processed into a fine powder, Mn (manganese) processed into a fine powder, Fe processed into a fine powder ( Iron), finely powdered Co (cobalt), finely powdered Ni (nickel), finely powdered Cu (copper), finely powdered Zn (zinc), finely powdered Processed Nb (niobium), finely powdered Mo (molybdenum), and finely powdered Ag (silver)) and a predetermined binder 51 (powder-like resin-based binder) are uniformly mixed. A dispersed fine metal powder mixture 59 is prepared, a predetermined pore forming material 58 (foaming agent) is added to (added to) the fine metal powder mixture 59, and the fine metal powder mixture 59 added with the fine pore forming material 58 is applied to a thin plate having a predetermined area. It is formed by molding (extrusion molding or injection molding) into a thin plate-shaped metal fine powder molded product 60, and degreasing and sintering (firing) the metal fine powder molded product 60 at a predetermined temperature ( (See FIG. 9).

In the anode 11 and the cathode 12, a metal-fine powder mixture 59 of a fine powder of a platinum group metal 49 so that the composite work function of the work functions of at least two selected transition metals 50 approximates the work function of a platinum group metal 49. Of the selected at least two kinds of transition metals 50 to the total weight of the metal fine powder mixture 59 are determined.

Specifically, the weight ratio of the platinum group metal 49 to the total weight (100%) of the platinum group metal fine powder to the metal fine powder mixture 59 is in the range of 4% to 10%, preferably in the range of 6% to 8%. And the weight ratio of one kind of transition metal fine powder among the selected transition metals 50 to the total weight (100%) of the metal fine powder mixture 59 is in the range of 45% to 48%, and the selected transition metal The weight ratio of the other transition metal fine powder of the metal 50 to the total weight (100%) of the fine metal powder mixture 59 is in the range of 45% to 48%.

Weight ratio of platinum group metal fine powder of platinum group metal 49, weight ratio of transition metal fine powder of one selected transition metal 50, weight of transition metal fine powder of another selected one kind of transition metal 50 When the ratio is out of the above range, the composite work function of the transition metal fine powders of the transition metals 50 cannot be approximated to the work function of the platinum group metal, and the metal fine powder mixture molded product 60 is obtained by molding the metal fine powder mixture 59. The anode 11 and the cathode 12 made by degreasing and sintering (sintering) cannot exhibit substantially the same catalytic activity (catalytic action) as the electrode supporting platinum.

The electrolysis device 10 includes a weight ratio of the fine powder of the platinum group metal 49 to the total weight of the fine metal powder mixture 59, a weight ratio of the fine powder of the selected transition metal 50, and a weight ratio of the other selected one. By setting the weight ratio of the fine particles of the transition metal 50 within the above range, the composite work function of the work functions of at least two selected transition metals 50 can be approximated to the work function of the platinum group metal, and the anode 11 And the cathode 12 has substantially the same work function as the electrode supporting platinum, the anode 11 and the cathode 12 have excellent catalytic activity (catalyst action), and the anode 11 and the cathode 12 are substantially the same as the electrode supporting platinum. By exhibiting the catalytic activity (catalytic action), the electrolysis can be efficiently performed using the anode 11 and the cathode 12, and a large amount of hydrogen gas can be generated in a short time.

A large number of fine pores 23 (flow paths) (continuous and independent passage holes) having different diameters are formed in the anode 11 and the cathode 12. The anode 11 and the cathode 12 have a large number of fine pores 23, and therefore have a large specific surface area. The pores 23 have a plurality of through holes 25 that open to the front surface 21 of the anode 11 and the cathode 12, and a plurality of through holes 25 that open to the rear surface 22 of the anode 11 and the cathode 12. The anode 11 and the cathode 12 penetrate in the thickness direction from the front surface 21 to the rear surface 22.

The pores 23 extend irregularly in the thickness direction of the anode 11 and the cathode 12 between the front surface 21 and the rear surface 22 of the anode 11 and the cathode 12, and extend from the outer peripheral edge 26 of the anode 11 and the cathode 12. It extends toward the center while irregularly bending in the radial direction of the anode 11 and the cathode 12. The pores 23 (flow passages) (continuous and independent passage holes) that are adjacent to each other in the radial direction and bend in the thickness direction are partially connected in the radial direction, and one pore 23 and the other pore 23 communicate with each other. is doing. The pores 23 (flow passages) (continuous and independent passage holes) that are adjacent to each other in the thickness direction and bend and extend in the radial direction are partially connected in the thickness direction, and one pore 23 and the other pore 23 communicate with each other. is doing.

The opening area (opening diameter) of the pores 23 is not uniform in the thickness direction, changes irregularly in the thickness direction, and is not uniform in the radial direction but in the radial direction. Are changing irregularly. The pores 23 open irregularly in the thickness direction and the radial direction while the opening area (opening diameter) increases or decreases. The opening areas (opening diameters) of the flow openings 25 opening on the front surface 21 and the back surface 22 of the anode 11 and the cathode 12 are not uniform, and the areas are all different. There is. The opening diameter (average opening diameter) of the pores 23 and the opening diameter (average opening diameter) of the through holes 25 of the front and rear surfaces 21, 22 are in the range of 1 μm to 100 μm.

In the electrolyzer 10, a plurality of pores 23 (flow paths) (continuous and independent passage holes) that extend while being irregularly bent in the thickness direction and the radial direction are formed in the anode 11 and the cathode 12 used therein. The anode 11 and the cathode 12 have a large specific surface area, and while the aqueous solution (liquid) flows through the pores 23, the aqueous solution (liquid) can be brought into wide contact with the contact surfaces of the pores 23 of the anode 11 and the cathode 12. It is possible to effectively and maximize the catalytic activity (catalytic action) of the cathode 11 and the cathode 12.

The thickness dimension L1 of the anode 11 and the cathode 12 (thin plate electrode 24 having a microporous structure) is in the range of 0.03 mm to 1.5 mm, preferably in the range of 0.05 mm to 1.0 mm. When the thickness dimension L1 of the anode 11 and the cathode 12 is less than 0.03 mm (0.05 mm), the strength thereof decreases, and the anode 11 and the cathode 12 are easily damaged or destroyed when an impact is applied, and the shapes thereof are May not be able to maintain. When the thickness dimension L1 of the anode 11 and the cathode 12 exceeds 1.5 mm (1.0 mm), the electric resistance of the anode 11 and the cathode 12 increases, and the current does not smoothly flow to the anode 11 and the cathode 12, so that the anode 11 and When the cathode 12 is used in the electrolyzer 10 (hydrogen gas generator), the electrolyzer 10 cannot efficiently perform electrolysis, and the electrolyzer 10 generates a large amount of hydrogen gas in a short time. I can't.

Since the thickness dimension L1 of the anode 11 and the cathode 12 used in the electrolyzer 10 is in the range of 0.03 mm to 1.5 mm, preferably 0.05 mm to 1.0 mm, the anode 11 and the cathode 12 are used. Has a high strength and can maintain its shape, and it is possible to prevent breakage or damage of the anode 11 or the cathode 12 when the anode 11 or the cathode 12 is impacted. Furthermore, the electric resistance of the anode 11 and the cathode 12 can be reduced, and a current smoothly flows through the anode 11 and the cathode 12, and when the anode 11 and the cathode 12 are used in the electrolyzer 10 (hydrogen gas generator). In addition, electrolysis can be efficiently performed in the electrolysis device 10, and a large amount of hydrogen gas can be generated in the electrolysis device 10 in a short time.

The porosity of the anode 11 and the cathode 12 (thin plate electrode 24 having a microporous structure) is in the range of 70% to 85%. When the porosity of the anode 11 and the cathode 12 is less than 70%, many fine pores 23 (continuous and independent passage holes) are not formed in the anode 11 and the cathode 12, and the specific surface area of the anode 11 and the cathode 12 is increased. I can't. When the porosity of the anode 11 and the cathode 12 exceeds 85%, the opening area (opening diameter) of the pores 23 (continuous and independent passage holes) and the opening area (opening diameter) of the flow ports 25 of the front and rear surfaces 21, 22 are reduced. It becomes larger than necessary, the strength of the anode 11 and the cathode 12 decreases, and the anode 11 and the cathode 12 are easily damaged or damaged when an impact is applied, and the shape thereof may not be maintained, and The catalytic action of the anode 11 and the cathode 12 is reduced, and the catalytic activity cannot be exhibited.

In the electrolyzer 10, since the porosities of the anode 11 and the cathode 12 (thin plate electrode 24 having a microporous structure) used for the electrolyzer 10 are within the above range, the anode 11 and the cathode 12 have a large opening area (opening diameter). The fine pores 23 (the pores 13 having an average diameter in the range of 1 to 100 μm) and the flow openings 25 (the average diameter in the range of 1 to 100 μm) of the numerous fine front and rear surfaces 21, 22 having different opening areas (opening diameters). It is formed into a porous (microporous structure) having a flow port 25), and the specific surface area of the anode 11 and the cathode 12 can be increased, and while the aqueous solution (liquid) flows through the pores 23, the aqueous solution (liquid) is discharged. The contact surfaces of the pores 23 of the anode 11 and the cathode 12 can be widely contacted, and the catalytic activity (catalytic action) of the anode 11 and the cathode 12 can be effectively and maximally utilized. Further, the catalytic action of the anode 11 and the cathode 12 is improved, and excellent catalytic activity can be exhibited in the anode 11 and the cathode 12, and the anode 11 and the cathode 12 are used in the electrolyzer 10 (hydrogen gas generator). In this case, the electrolysis device 10 can efficiently perform electrolysis, and the electrolysis device 10 can generate a large amount of hydrogen gas in a short time.

Electrolyzer 10 has a density of 6.0g ^/ cm ² ~8.0g ^/ cm 2 range (thin plate electrode 24 of the micro-porous structure) anode 11 and cathode 12 for use therewith, preferably, 6.5 g / cm It is in the range of ^{2 to} 7.5 g/cm ² . When the densities of the anode 11 and the cathode 12 are less than 6.0 g/cm ² (6.5 g/cm ² ), the strength of the anode 11 and the cathode 12 decreases, and the anode 11 and the cathode 12 are easily formed when an impact is applied. In some cases, it may be damaged or damaged and the shape thereof may not be maintained, and the catalytic action of the anode 11 and the cathode 12 may be deteriorated and the catalytic activity may not be exhibited. When the densities of the anode 11 and the cathode 12 exceed 8.0 g/cm ² (7.5 g/cm ² ), many fine pores 23 and many fine flow holes 25 are formed in the anode 11 and the cathode 12. In addition, the specific surface area of the anode 11 or the cathode 12 cannot be increased, and the catalytic action of the anode 11 or the cathode 12 is lowered, so that the catalytic activity (catalytic action) of the anode 11 or the cathode 12 cannot be effectively used. ..

In the electrolyzer 10, since the densities of the anode 11 and the cathode 12 used therein are within the above range, the anode 11 and the cathode 12 have a large number of fine pores 23 (average diameter of 1 to 100 μm) having different opening areas (opening diameters). Of pores 23) and a large number of minute front and rear surfaces 21 and 22 having different opening areas (opening diameters) through holes 25 (through holes 25 having an average diameter in the range of 1 to 100 μm) are porous (micro). Porous structure), the specific surface area of the anode 11 and the cathode 12 can be increased, and the aqueous solution (liquid) flows through the pores 23 while the aqueous solution (liquid) contacts the pores 23 of the anode 11 and the cathode 12. It can be widely contacted with the surface, the catalytic action of the anode 11 and the cathode 12 is improved, and the catalytic activity (catalytic action) of the anode 11 and the cathode 12 can be effectively and maximally utilized.

In the electrolyzer 10, by setting the densities of the anode 11 and the cathode 12 used therein to the above range, the anode 11 and the cathode 12 have a large number of fine pores 23 having different opening areas (opening diameters) and opening areas (opening diameters). ) Are formed into a porous structure having a plurality of minute front and rear surfaces 21 and 22 through holes 25, the specific surface area of the anode 11 and the cathode 12 can be increased, and the pores 23 can be passed by an aqueous solution (liquid). It becomes possible to bring the aqueous solution (liquid) into wide contact with the contact surfaces of the pores 23 of the anode 11 and the cathode 12 while flowing, and the catalytic activity (catalytic action) substantially the same as that of the electrode in which the anode 11 and the cathode 12 contain a platinum group metal. Can be reliably exhibited, and electrolysis can be efficiently performed using the anode 11 and the cathode 12, and a large amount of hydrogen gas can be generated in a short time.

Fine powder of Pt (Pt processed into powder), Fine powder of Pb (Pb processed into powder), Fine powder of Rh (Rh processed into powder), Fine powder of Ru (in powder form) Processed Ru), Ir fine powder (Ir processed into powder), Os fine powder (Os processed into powder), Ti fine powder (Ti processed into powder), Cr Fine powder (Cr processed into powder), Mn fine powder (Mn processed into powder), Fe fine powder (Fe processed into powder), Co fine powder (processed into powder) Co), Ni fine powder (Ni processed into powder), Cu fine powder (Cu processed into powder), Zn fine powder (Zn processed into powder), Nb fine powder The particle size of (powder-processed Nb), Mo fine powder (powder-processed Mo), and Ag fine powder (powder-processed Ag) is in the range of 1 μm to 100 μm.

When the particle size of the fine particles of the platinum group metal 49 or the particle size of the fine particles of the transition metal 50 is less than 1 μm, the fine particles of these metals block the pores 23 (continuous and independent passage holes), and the anode 11 and A large number of fine pores 23 cannot be formed in the cathode 12, the specific surface area of the anode 11 and the cathode 12 cannot be increased, and the catalytic action of the anode 11 and the cathode 12 decreases, so that the anode 11 and the cathode 12 It is impossible to effectively utilize the catalytic activity (catalytic action) of. When the particle size of the fine particles of the platinum group metal 49 or the particle size of the fine particles of the transition metal 50 exceeds 100 μm, the opening area (opening diameter) of the pores 23 and the openings of the flow ports 25 of the front and rear surfaces 21, 22 are formed. The area (opening diameter) becomes unnecessarily large, many fine pores 23 cannot be formed in the anode 11 and the cathode 12, the specific surface area of the anode 11 and the cathode 12 cannot be increased, and the anode 11 Moreover, the catalytic action of the cathode 12 is lowered, and the catalytic activity (catalytic action) of the anode 11 and the cathode 12 cannot be effectively utilized.

In the electrolyzer 10, since the particle size of the fine particles of the platinum group metal 49 and the particle size of the transition metal 50 that form the anode 11 and the cathode 12 are within the above range, the opening area of the anode 11 and the cathode 12 ( A large number of fine pores 23 having different opening diameters (pores 25 having an average diameter in the range of 1 to 100 μm) and a large number of fine front and rear surfaces 21 and 22 having different opening areas (opening diameter) through holes 25 (average diameter) Is formed into a porous (microporous structure) having a flow port 25) in the range of 1 to 100 μm, and the specific surface area of the anode 11 and the cathode 12 can be increased, and the pores 23 are allowed to pass through an aqueous solution (liquid). While flowing, the aqueous solution (liquid) can be brought into wide contact with the contact surfaces of the pores 23 of the anode 11 and the cathode 12, and the catalytic activity (catalytic action) of the anode 11 and the cathode 12 can be effectively and maximally utilized. it can. Further, the catalytic action of the anode 11 and the cathode 12 is improved, and excellent catalytic activity can be exhibited in the anode 11 and the cathode 12, and the anode 11 and the cathode 12 are used in the electrolyzer 10 (hydrogen gas generator). In this case, the electrolysis device 10 can efficiently perform electrolysis, and the electrolysis device 10 can generate a large amount of hydrogen gas in a short time.

Specific examples of the platinum group metal 49 and the transition metal 50 used for the anode 11 and the cathode 12 (thin plate electrode 24 having a microporous structure) include Pt 52 (platinum) processed into powder as shown in FIG. Fine powder 55 (particle diameter: 1 μm to 100 μm), fine powder Ni53 (nickel) fine powder 56 (particle diameter: 1 μm to 100 μm), and fine powder processed Fe54 (iron) fine powder 57 (particle size: 1 μm to 100 μm) is used as a raw material.

For the anode 11 and the cathode 12, a fine metal powder mixture 59 is prepared by uniformly mixing and dispersing fine powders 55 to 57 of Pt 52, Ni 53, and Fe 54 and a predetermined binder 51, and the fine pore powder forming material 58 ( Foaming agent), and the fine metal powder mixture 59 to which the pore forming material 58 is added is molded (extrusion molding or injection molding) into a thin plate having a predetermined area to form a fine metal powder molding 60, and the fine metal powder molding is performed. By degreasing the object 60 and sintering (baking) at a predetermined temperature, a thin plate-like electrode having a microporous structure in which a large number of fine pores 23 (pores 23 having an average diameter in the range of 1 to 100 μm) are formed Molded.

In the anode 11 and the cathode 12, all of the metal fine powder mixture 59 of the platinum group metal fine powder 55 of Pt 52 is made so that the combined work function of the work function of Ni 53 and the work function of Fe 54 approximates the work function of the platinum group metal. The weight ratio to the weight, the weight ratio of the transition metal fine powder 56 of Ni53 to the total weight of the metal fine powder mixture 59, and the weight ratio of the transition metal fine powder 57 of Fe54 to the total weight of the metal fine powder mixture 59 are determined.

The weight ratio of the platinum group metal fine powder 55 of Pt52 (platinum group metal 49) to the total weight (100%) of the metal fine powder mixture 59 is in the range of 4% to 10%, preferably in the range of 5% to 8%. The weight ratio of the transition metal fine powder 56 of Ni53 (transition metal 50) to the total weight (100%) of the fine metal powder mixture 59 is in the range of 45% to 48%. The weight ratio of the transition metal fine powder 57 of Fe 54 (transition metal 50) to the total weight (100%) of the metal fine powder mixture 59 is in the range of 45 to 48%.

When the weight ratio of the platinum group metal fine powder 55 of Pt52, the weight ratio of the transition metal fine powder 56 of Ni53, and the weight ratio of the transition metal fine powder 57 of Fe54 are out of the above ranges, the fine powder 56 of Ni53 and the fine powder of Fe54 are The composite work function of 57 and the work function of the platinum group metal cannot be approximated, and the anode 11 and the cathode 12 made by degreasing and sintering the metal fine powder molded product 60 obtained by molding the metal fine powder mixture 59. Cannot exhibit substantially the same catalytic activity (catalytic action) as the electrode supporting platinum.

The electrolyzer 10 sets the weight ratio of the Pt 52 fine powder 55, the Ni 53 fine powder 56, and the Fe 54 fine powder 57 to the total weight of the metal fine powder mixture 59 within the above range. The composite work function of the work functions of the transition metals 50 of various kinds can be approximated to the work function of the platinum group metal, and the anode 11 and the cathode 12 have substantially the same work function as the electrode supporting the platinum group metal, and the anode 11 Since the cathode 11 and the cathode 12 have excellent catalytic activity (catalytic action), and the anode 11 and the cathode 12 exhibit substantially the same catalytic activity (catalytic action) as the electrode supporting platinum, the anode 11 and the cathode 12 are used. The electrolysis can be efficiently performed, and a large amount of hydrogen gas can be generated in a short time.

FIG. 4 is a diagram illustrating an example of electrolysis using the electrolyzer 10, and FIG. 5 is a diagram illustrating an example of a hydrogen gas generation system 27 using the electrolyzer 10. In the electrolysis shown in FIG. 4, water (aqueous solution) is electrolyzed to generate hydrogen and oxygen. However, in addition to water (H ₂ O), the electrolysis device 10 is used to generate an aqueous solution of NaOH, H Electrolysis of ₂ SO ₄ aqueous solution, NaCl aqueous solution, AgNO ₃ aqueous solution, and CuSO ₄ aqueous solution is performed.

In the electrolysis of water in the electrolyzer 10, as shown by the arrows in FIG. 4, water (H ₂ O) is supplied to the anode water storage tank 16 and the cathode water storage tank 17, and the anode main electrode 18 is supplied from the power source + The current is supplied to the cathode main electrode 19 as well as the negative current from the power supply. The positive current supplied to the anode main electrode 18 is supplied from the anode power supply member 14 to the anode 11 (anode), and the negative current supplied to the cathode main electrode 19 is supplied from the cathode power supply member 15 to the cathode 12 (cathode). To be done.

At the anode 11 (electrode), oxygen is generated by the anodic reaction (catalytic action) of 2H ₂ O→4H ⁺ +4e ⁻ +O ₂ , and at the cathode 12 (electrode), the cathodic reaction of 4H ⁺ +4e ⁻ →2H ₂ (catalytic action). ) Produces hydrogen. Protons (hydrogen ions: H ⁺ ) move through the solid polymer electrolyte membrane 13 from the anode 11 to the cathode 12 (electrode). Protons generated at the anode 11 flow through the solid polymer electrolyte membrane 12.

In the electrolyzer 10, the anode 11 (electrode) and the cathode 12 (electrode) include fine powder of platinum group metal 49, and further, the work functions of at least two kinds of transition metals 50 forming the anode 11 and the cathode 12 are synthesized. At least two kinds of transition metals 50 are selected from the transition metals 50 so that the work function is close to the work function of the platinum group metal, and the composite work function of the work functions of the selected transition metals 50 is the platinum group metal. The weight ratio of the platinum group metal 49 to the total weight of the fine metal powder mixture 59 is determined so as to approximate the work function, and the weight ratio of at least two selected transition metals 50 to the total weight of the fine metal powder mixture 59 is determined. Since the anode 11 and the cathode 12 have substantially the same work function as that of the platinum-supported electrode, they exhibit substantially the same catalytic activity (catalytic action) as the platinum-supported electrode, and hydrogen is a proton and an electron. And can be decomposed efficiently.

The anode 11 and the cathode 12 shown as specific examples include fine powder 55 of Pt 52, and Ni53 and Fe54 are selected and selected so that the composite work function of the work functions approximates the work function of the platinum group metal. The weight ratio of the fine powder 55 of Pt52 to the total weight of the fine metal powder mixture 59 is determined such that the total work function of the work functions of the Ni53 and Fe54 is approximated to the work function of the platinum group metal. Since the weight ratio of the fine powder 56 of Ni53 to the total weight of the mixture 59 and the weight ratio of the fine powder 57 of Fe54 to the total weight of the metal fine powder mixture 59 are determined, the anode 11 and the cathode 12 are Has a work function substantially the same as that of the electrode supporting platinum, exhibits substantially the same catalytic activity (catalytic action) as the electrode supporting platinum, and hydrogen is efficiently decomposed into protons and electrons.

In the electrolysis of the NaOH aqueous solution, an anode reaction (catalytic action) of 4OH ⁻ →2H ₂ O+O ₂ +4e ⁻ occurs at the anode 11, and a cathode reaction (catalytic action) of 2H ₂ O+2e ⁻ →2OH ⁻ +H _{2 at} the cathode 12. Happens. In the electrolysis of the H ₂ SO ₄ aqueous solution, an anodic reaction (catalytic action) of 2H ₂ O→O ₂ +4H ⁺ +4e ⁻ occurs in the anode 11, and a cathodic reaction of 2H ⁺ +2e ⁻ →H _{2 in} the cathode 12 (catalytic action). Happens.

In the electrolysis of an aqueous NaCl solution, an anode reaction of 2Cl ⁻ →Cl ₂ +2e ⁻ (catalytic action) occurs at the anode 11, and a cathode reaction of 2H ₂ O+2e ⁻ →2OH ⁻ +H ₂ occurs at the cathode 12 (catalytic action). In the electrolysis of the AgNO ₃ aqueous solution, an anodic reaction (catalytic action) of 2H ₂ O→O ₂ +4H ⁺ +4e ⁻ occurs at the anode 11, and a cathodic reaction (catalytic action) of Ag ⁺ +e ⁻ →Ag occurs at the cathode 12. In the electrolysis of the CuSO ₄ aqueous solution, an anodic reaction (catalytic action) of 2H ₂ O→O ₂ +4H ⁺ +4e ⁻ occurs at the anode 11, and a cathodic reaction (catalytic action) of Cu ²⁺ +2e ⁻ →Cu occurs at the cathode 12.

The hydrogen gas generation system 27 includes a DC power supply 28 for supplying electricity to the electrolyzer 10, an anode 11 and a cathode 12 of the electrolyzer 10, a water storage tank 29 for storing water (pure water), and water (pure water). A water supply pump 30 for supplying water), an oxygen gas-liquid separator 31, two circulation pumps 32, 33 for supplying water (pure water), a hydrogen gas-liquid separator 34, and a cylinder 35 for storing hydrogen ( Hydrogen tank).

In the hydrogen gas generation system 27, the water (pure water) stored in the water storage tank 29 is supplied to the oxygen gas-liquid separator 31 by the water supply pump 30, and the water flowing out from the oxygen gas-liquid separator 31 is supplied to the electrolyzer 10. Water is supplied. Electricity is supplied from the DC power supply 28 to the electrolyzer 10, and electrolysis is performed in the electrolyzer 10 to decompose water into hydrogen and oxygen. Oxygen flows into the oxygen gas-liquid separator 31, is separated into gas and liquid, and is then released to the atmosphere. The water that has been gas-liquid separated in the oxygen gas-liquid separator 31 is supplied to the electrolyzer 10 again by the circulation pump 32. Hydrogen flows into the hydrogen gas-liquid separator 34, is gas-liquid separated, and then flows into the cylinder 35 (hydrogen tank). The water that has been gas-liquid separated in the hydrogen gas-liquid separator 34 is supplied to the electrolyzer 10 again by the circulation pump 33.

In the electrolyzer 10 (hydrogen gas generation system 27), the anode 11 and the cathode 12 used therein have a composite work function of the work functions of the platinum group metal 49 and the predetermined transition metal 50, and the work function approximates to the work function of the platinum group metal. A fine metal powder mixture 59 is prepared by uniformly mixing and dispersing at least two kinds of transition metals 50 selected as described above and a predetermined binder 51 (powder-like resin binder), and the fine metal powder mixture 59 has predetermined pores. A thin plate-shaped metal fine powder molding by adding (adding) the forming material 58 (foaming agent) and molding (extrusion molding or injection molding) the fine metal powder mixture 59 to which the pore forming material 58 is added into a thin plate having a predetermined area. A thin plate-like electrode 24 having a microporous structure in which a large number of fine pores 23 and flow ports 25 are formed by making a metal 60, degreasing and sintering (baking) the metal fine powder molded product 60. The weight ratio of the platinum group metal 49 to the total weight of the fine metal powder mixture 59 is determined so that the composite work function of the transition metal 50 and the work function of the platinum group metal is approximated. Since the weight ratio of the transition metals 50 to the total weight is determined, the anode 11 and the cathode 12 have substantially the same work function as the electrode supporting platinum, and the anode 11 and the cathode 12 have excellent catalytic activity (catalytic action). ), and the anode 11 and the cathode 12 exhibit substantially the same catalytic activity (catalyst action) as the electrode supporting platinum, so that the electrolysis can be efficiently performed using the anode 11 and the cathode 12. Therefore, a large amount of hydrogen gas can be generated in a short time.

Further, Pt52 (platinum) as the platinum group metal 49 is used as a raw material, and Ni53 (nickel) and Fe54 (iron) are used as the transition metal 50 as raw materials. In 27), Ni53 and Fe54 are selected so that the composite work function of the work functions of the transition metal 50 approximates the work function of the platinum group metal, and the total work function of the selected work functions of Ni53 and Fe54 is The weight ratio of the fine powder 55 of Pt52 to the total weight of the fine metal powder mixture 59 is determined so as to approximate the work function of the platinum group metal, and the weight ratio of the fine powder 56 of Ni53 to the total weight of the fine metal powder mixture 59 is determined. And the weight ratio of the fine powder 57 of Fe54 are determined, the anode 11 and the cathode 12 have substantially the same work function as the electrode supporting platinum, and the anode 11 and the cathode 12 have excellent catalytic activity (catalytic action). ), and the anode 11 and the cathode 12 exhibit substantially the same catalytic activity (catalyst action) as the electrode supporting platinum, so that the electrolysis can be efficiently performed using the anode 11 and the cathode 12. Therefore, a large amount of hydrogen gas can be generated in a short time.

In the electrolyzer 10 (hydrogen gas generation system 27), the thickness dimension L1 of the anode 11 and the cathode 12 is in the range of 0.03 mm to 1.5 mm, preferably in the range of 0.05 mm to 1.0 mm. The electric resistances of the cathode 11 and the cathode 12 can be reduced, a current can be smoothly passed through the anode 11 and the cathode 12, and the electrolysis can be reliably performed by using the anode 11 and the cathode 12.

In the electrolyzer 10 (hydrogen gas generation system 27), the anode 11 and the cathode 12 include an inexpensive transition metal 50 (for example, Ni53, Fe54) selected from various transition metals 50, and the entire metal fine powder mixture 59 is contained. The weight ratio of the fine powder of the transition metal 50 to the weight (the weight ratio of the fine powder 56 of Ni53, the weight ratio of the fine powder 57 of Fe54) is within the above range, and the platinum group metal 49 to the total weight of the fine metal powder mixture 59 is 49. The weight ratio of the fine powder of (5) (the weight ratio of the fine powder 55 of Pt52) is within the above range, and the content of the expensive platinum group metal 49 (Pt52) is small, so that the material cost of the anode 11 and the cathode 12 can be reduced. Therefore, the electrolyzer 10 (hydrogen gas generation system 27) can be manufactured at low cost, and the operating cost of the electrolyzer 10 (hydrogen gas generation system 27) can be reduced.

FIG. 6 is a side view of a polymer electrolyte fuel cell 36 using an air electrode 38 (anode 11) and a fuel electrode 37 (cathode 12), and FIG. 7 is a side view of the anode 11 (air electrode 38) and the cathode 12 ( It is a figure which shows the result of the electromotive voltage test of the fuel electrode 37). FIG. 8 is a diagram showing the results of the IV characteristic test of the anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37). FIG. 6 shows a state in which the load 48 is connected, but in the electromotive voltage test, the load 48 does not exist and there is no load. In the electromotive voltage test and the IV characteristic test, the anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) used in the electrolyzer 10 were used in the polymer electrolyte fuel cell 36 shown in FIG. The electromotive voltage was measured under a load, the load 48 was connected to the polymer electrolyte fuel cell 36, and the IV characteristic was measured.

As shown in FIG. 6, the polymer electrolyte fuel cell 36 includes a fuel electrode 37 (cathode 12) and an air electrode 38 (anode 11), and a solid height position (interposition) between the fuel electrode 37 and the air electrode 38. The molecular electrolyte membrane 39 (electrode assembly membrane) (fluorine-based ion exchange membrane having a sulfonic acid group), the separator 40 (bipolar plate) located on the outer side in the thickness direction of the fuel electrode 37, and the outer side in the thickness direction of the air electrode 38. It is formed from the separator 41 (bipolar plate) located.

A supply channel for a reaction gas (hydrogen, oxygen, etc.) is engraved (engraved) on the separators 40, 41. The fuel electrode 37, the air electrode 38, and the solid polymer electrolyte membrane 39 are overlapped and integrated in the thickness direction to form a membrane/electrode assembly 42 (Membrane Electrode Assembly, MEA), and the membrane/electrode assembly 42 is separated by the separator 40. , 41 are sandwiched. The solid polymer electrolyte membrane 39 has proton conductivity and no electron conductivity.

A gas diffusion layer 43 is formed between the fuel electrode 37 and the separator 40, and a gas diffusion layer 44 is formed between the air electrode 38 and the separator 41. Gas seals 45 are installed between the fuel electrode 37 and the separator 40 and above and below the gas diffusion layer 43. Gas seals 46 are installed between the air electrode 38 and the separator 41 and above and below the gas diffusion layer 44.

In the polymer electrolyte fuel cell 36, hydrogen (fuel) is supplied to the fuel electrode 37 (cathode 12) and air (oxygen) is supplied to the air electrode 38 (anode 11). At the fuel electrode 37, hydrogen is decomposed into protons (hydrogen ions, H ⁺ ) and electrons by the reaction (catalysis) of H ₂ →2H ⁺ +2e ⁻ . Thereafter, the protons move from the fuel electrode 37 to the air electrode 38 through the solid polymer electrolyte membrane 39, and the electrons move to the air electrode 38 through the lead wire 47. Protons generated at the fuel electrode 37 flow through the solid polymer electrolyte membrane 39. At the air electrode 38, the protons that have moved from the solid polymer electrolyte membrane 39 and the electrons that have moved through the lead wire 47 react with oxygen in the air, and water is produced by the reaction of 4H ⁺ +O ₂ +4e→2H ₂ O.

In the polymer electrolyte fuel cell 36, a fuel electrode 37 (cathode 12) and an air electrode 38 (anode 12) contain fine powder of platinum group metal 49, and a transition metal 50 forming the fuel electrode 37 and the air electrode 38. At least two kinds of transition metals 50 are selected from the transition metals 50 so that the composite work function of the selected transition metals 50 is close to the work function of the platinum group metal. Is determined to approximate the work function of the platinum group metal, the weight ratio of the fine powder of platinum group metal 49 to the total weight of the fine metal powder mixture 59 is determined, and the fine metal mixture of the fine powder of transition metal 50 is selected. Since the weight ratio of 59 to the total weight is determined, the fuel electrode 37 and the air electrode 38 have substantially the same work function as that of the platinum-supported electrode, and have substantially the same catalytic activity (catalytic action) as the platinum-supported electrode. ), hydrogen is efficiently decomposed into protons and electrons.

The fuel electrode 37 (cathode 12) and the air electrode 38 (anode 12) of the polymer electrolyte fuel cell 36 shown as a specific example contain the platinum group metal fine powder 55 of Pt 52, and the work function of the composite work function is Ni53 and Fe54 are selected so as to approximate the work function of the platinum group metal, and the fine metal powder is selected so that the total work function of the selected work functions of Ni53 and Fe54 approximates the work function of the platinum group metal. The weight ratio of the Pt 52 fine powder 55 to the total weight of the mixture 59 is determined, the weight ratio of the Ni 53 fine powder 56 to the total weight of the metal fine powder mixture 59 is determined, and the total weight of the metal fine powder mixture 59 is determined. Since the weight ratio of the fine powder 57 of Fe54 to that of Fe is determined, the fuel electrode 37 and the air electrode 38 have substantially the same work function as the electrode supporting platinum, and the catalytic activity is substantially the same as that of the electrode supporting platinum. (Catalytic action), and hydrogen is efficiently decomposed into protons and electrons.

In the electromotive voltage test, the voltage (V) between the electrodes (fuel electrode 37 and air electrode 38) and the electrodes (fuel electrode 37 and air electrode 38) (between electrodes) for 15 minutes after hydrogen gas was injected. Was measured. In the diagram showing the results of the electromotive force test in FIG. 7, the horizontal axis represents the measurement time (min), and the vertical axis represents the electrodes (fuel electrode 37 and air electrode 38) and electrodes (fuel electrode 37 and air electrode 38). The voltage (V) between the electrodes (between the electrodes) is represented. In the polymer electrolyte fuel cell 36 using the fuel electrode 37 (cathode 12) and the air electrode 38 (anode 12), as shown in FIG. 7, the voltage between the electrodes is 1.07 (V) to 1.088 ( V).

In the IV characteristic test, a load 48 is connected between the electrodes (fuel electrode 37 or air electrode 38) and the electrodes (fuel electrode 37 or air electrode 38) (between the electrodes), and the relationship between voltage and current is measured. did. In the diagram showing the results of the IV characteristic test in FIG. 8, the horizontal axis represents current (A) and the vertical axis represents voltage (V). In the polymer electrolyte fuel cell 36 using the fuel electrode 37 (cathode 12) and the air electrode 38 (anode 12), a gradual voltage drop was observed as shown in FIG. As shown in the results of the electromotive force test of FIG. 7 and the results of the IV characteristic test of FIG. 8, a reaction in which the fuel electrode 37 (cathode 12) and the air electrode 38 (anode 12) emit electrons to become hydrogen ions. It was confirmed that it has an excellent oxygen reduction function (catalytic action) as well as an excellent catalytic action for promoting oxygen.

FIG. 9 is a diagram illustrating a method of manufacturing the anode 11 and the cathode 12 used in the electrolyzer 10. As shown in FIG. 9, the anode 11 and the cathode 12 include a metal selecting step S1, a metal fine powder producing step S2, a fine powder weight ratio determining step S3, a metal fine powder mixture producing step S4, and a metal fine powder molded article producing step S5. , Is manufactured by an electrode manufacturing method including a microporous thin plate electrode forming step S6. In the electrode manufacturing method, the anode 11 (air electrode 38) and the cathode 12 (fuel electrode) used in the electrolyzer 10 (solid polymer fuel cell 36) using the platinum group metal 49 and at least two kinds of transition metals 50 as raw materials. 37) is produced.

In the metal selection step S1, at least one platinum group metal 49 (platinum (Pt), palladium (Pb), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium is selected from among various platinum group metals 49. (Os)) is selected and selected from various transition metals 50. Among the various transition metals 50, the composite work functions of the work functions of at least two transition metals 50 are approximated to the work functions of platinum group metals. To at least two kinds of transition metals 50 (Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Nb (Niobium), Mo (molybdenum), Ag (silver)) is selected. In addition, Pt52 (platinum) is selected as the platinum group metal 49 used for the anode 11 and the cathode 12, and Ni53 (nickel) and Fe54 (iron) are selected as the transition metal 50 used for the anode 11 and the cathode 12. To do.

In the fine metal powder preparation step S2, platinum 52 (Pt) is finely pulverized by a fine pulverizer to a particle size of 1 μm to 100 μm, and a platinum group metal fine powder 55 of Pt 52 having a particle size of 1 μm to 100 μm is produced. Ni53 (nickel) is finely pulverized to a particle size of 1 μm to 100 μm to make a transition metal fine powder 56 of Ni53 having a particle size of 1 μm to 100 μm, and Fe54 (iron) is grained to a particle size of 1 μm to 100 μm by a fine pulverizer. Then, the transition metal fine powder 57 of Fe54 having a particle diameter of 1 μm to 100 μm is prepared.

The electrode manufacturing method is to pulverize Pt52 (platinum group metal 49), Ni53 (transition metal 50), and Fe54 (transition metal 50) to a particle size of 1 μm to 100 μm to obtain a large number of fine pores 23 (passage holes). It is possible to form a thin plate-shaped anode 11 or cathode 12 having a porous structure having a large specific surface area and having a large specific surface area, and the aqueous solution (liquid) while the aqueous solution (liquid) or gas (gas) flows through the pores 23. The anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) capable of widely contacting the contact surfaces in the pores 23 of the anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) with a gas or gas. ) Can be made.

In the fine powder weight ratio determining step S3, the combined work function of the work functions of the Ni53 fine powder 56 and the Fe54 fine powder 57 produced in the metal fine powder producing step S2 is approximated to the work function of the platinum group metal. The weight ratio of the Pt 52 fine powder 55 to the total weight of the metal fine powder mixture 59 is determined, and the weight ratio of the Ni 53 fine powder 56 to the total weight of the metal fine powder mixture 59 is determined. The weight ratio of the fine powder 57 of Fe54 to the total weight is determined.

In the fine powder weight ratio determining step S3, the weight ratio of the fine powder 55 of Pt52 (platinum group metal 49) to the total weight (100%) of the metal fine powder mixture 59 is in the range of 4% to 10%, preferably 5%. Determine in the range of ~8%. In the fine powder weight ratio determining step S3, the weight ratio of the fine powder 56 of Ni53 (transition metal 50) to the total weight (100%) of the metal fine powder mixture 59 is determined within the range of 45% to 48%. The weight ratio of the fine powder 57 of Fe54 (transition metal 50) to the total weight (100%) of the mixture 59 is determined in the range of 45% to 48%.

The electrode manufacturing method selects Ni53 (nickel) and Fe54 (iron) of the transition metal 50 so that the synthetic work function approximates the work function of the platinum group metal, and the synthetic work function is the work function of the platinum group metal. Similarly, the weight ratio of the fine powder 55 of Pt 52 to the total weight of the fine metal powder mixture 59, the weight ratio of the fine powder 56 of Ni 53 to the total weight of the fine metal powder mixture 59, and the total weight of the fine metal powder mixture 59 are similar. By determining the weight ratio of the fine powder 57 of Fe54 in the above range, the composite work function of the work functions of the fine powder 56 of Ni53 and the fine powder 57 of Fe54 can be approximated to the work function of the platinum group metal, Despite having a low content of platinum group metal 49 (Pt52), it has a work function substantially the same as that of the electrode supporting platinum and exhibits substantially the same catalytic activity (catalytic action) as the electrode supporting platinum. And an anode 11 (air electrode 38) and a cathode 12 (fuel electrode 37) containing a small amount of a platinum group metal, which are capable of providing excellent catalytic activity (catalyst action) and can sufficiently and reliably utilize the catalytic function. Can be made.

The electrode manufacturing method includes a weight ratio of the fine powder 56 of Ni53 (transition metal 50) to the total weight of the fine metal powder mixture 59 and a weight ratio of fine powder 57 of Fe54 (transition metal 50) to the total weight of the fine metal powder mixture 59. Is in the above range, and the weight ratio of the fine powder 55 of Pt52 (platinum group metal 49) to the total weight of the fine metal powder mixture 59 is in the above range. Therefore, the content of expensive platinum group metal 49 (Pt52) is small. The anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) can be manufactured at low cost.

In the fine metal powder mixture forming step S4, the fine powder 55 of Pt52 having the weight ratio determined in the fine powder weight ratio determining step S3 and the fine powder 56 of Ni53 and fine powder weight having the weight ratio determined in the fine powder weight ratio determining step S3. The fine powder 57 of Fe54 and the binder 51 (powder-like resin binder) having the weight ratio determined in the ratio determining step S3 are charged into a mixer, and the fine powder 55 of Pt52, the fine powder 56 of Ni53, and the Fe54 are mixed by the mixer. The fine powder 57 of No. 5 and the binder 51 are agitated and mixed, and the fine powder 55 of Pt 52, the fine powder 56 of Ni 53, the fine powder 57 of Fe 54, and the fine metal powder mixture 59 in which the binder 51 is uniformly mixed and dispersed (foam metal molding material). )make. Next, a predetermined amount of pore forming material 58 (powder blowing agent) is added to the metal fine powder mixture 59. A fine metal powder mixture 59 (foam metal molding material) in which a predetermined amount of pore forming material 58 is put into a mixer or stirrer and the fine metal powder mixture 59 is uniformly mixed and dispersed by the mixer or stirrer. make. The average diameter and porosity of the pores 25 formed in the anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) are determined by the addition amount of the pore forming material 58 (powder of powder).

In the metal fine powder molded product producing step S5, the metal fine powder mixture 59 (foam metal molding material) produced in the metal fine powder mixture producing step S4 is injected into an injection molding machine (not shown) or an extrusion molding machine (not shown). And the metal fine powder mixture 59 is injection-molded by an injection molding machine (metal powder injection molding), or the metal fine powder mixture 59 is extruded by an extrusion molding machine (metal powder extrusion molding). Metal fine powder molded product 60 (foamed metal molded product) formed by molding 59 into a thin plate having a predetermined area (thickness dimension L1 is in the range of 0.03 mm to 1.5 mm, preferably 0.05 mm to 1.0 mm). make.

In the microporous structure thin plate electrode producing step S6, the metal fine powder molded article 60 (foamed metal molded article) produced by the metal powder injection molding or the metal powder extrusion molding in the metal fine powder molded article producing step S5 is degreased and degreased. The metal fine powder molded product 60 is put into a firing furnace (combustion furnace, electric furnace, etc.), and the metal fine powder molded product 60 is sintered (fired) at a predetermined temperature for a predetermined time in the firing furnace to obtain a large number of fine pores 23 ( Anode 11 (air electrode 38) and cathode having a microporous structure and a thin plate shape (thickness dimension L1 is in the range of 0.03 mm to 1.5 mm, preferably in the range of 0.05 mm to 1.0 mm) in which passage holes are formed. 12 (fuel electrode 37) is made.

The sintering temperature is 900°C to 1400°C. The sintering (firing) time is 2 to 6 hours. In the microporous structure thin plate electrode forming step S6, the pore forming material 58 (powder foaming agent) is formed inside the metal fine powder molded product 60 when the metal fine powder molded product 60 molded into a thin plate having a predetermined area is sintered. After the foaming, the pore-forming material 58 disappears from the inside of the fine metal powder product 60, and a large number of fine pores 23 (flow paths) (continuous and independent passage holes) are formed to have a microporous structure and a thin plate shape. The anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) are manufactured.

In the electrode manufacturing method, the fine powder 55 of Pt 52, the fine powder 56 of Ni 53, and the fine powder 57 of Fe 54 are connected via the binder 51 by metal powder injection molding or metal powder extrusion molding, and metal powder injection molding or metal powder extrusion is performed. The metal fine powder molded product 60 (foamed metal molded product) formed by molding has a predetermined strength, and has a large number of fine pores 23 (passage holes) by sintering the metal fine powder molded product 60. The thin plate-shaped anode 11 (air electrode 38) and cathode 12 (fuel electrode 37) having a micro-porous structure can be formed, and the shape can be maintained with high strength, so that when the impact is applied, A non-platinum anode 11 (air electrode 38) and cathode 12 (fuel electrode 37) that can prevent breakage and damage can be made.

The electrode manufacturing method is to select at least one kind of platinum group metal 49 (Pt52) from among various kinds of platinum group metals 49, and select a work function of at least two kinds of transition metals 50 selected from various kinds of transition metals 50. The metal selection step S1 for selecting at least two kinds of transition metals 50 (for example, Ni53, Fe54) from the various transition metals 50 so that the function approximates the work function of the platinum group metal, and the metal selection step S1. At least one selected platinum group metal 49 (Pt52) is pulverized to form a platinum group metal fine powder (fine powder 55 of Pt52), and at least two transition metals 50 selected in the metal selection step S1 are obtained. A fine metal powder preparation step S2 for finely pulverizing the fine transition metal powder (fine powder 56 of Ni53, fine powder 57 of Fe54) and at least two kinds of fine transition metal powders produced by the fine metal powder preparation step S2. Work function composition so that the work function approximates the work function of the platinum group metal, and the weight ratio of the platinum group metal fine powder (fine powder 55 of Pt52) and at least two kinds of transition metal fine powder (fine powder 56 of Ni53, The fine powder weight ratio determining step S3 for determining the weight ratio of the fine powder 57) of Fe54, and the platinum group metal fine powder (fine powder 55 of Pt52) and at least 2 of the weight ratio determined in the fine powder weight ratio determining step S3. A predetermined binder 51 is added to various kinds of fine transition metal powders (fine powder 56 of Ni53, fine powder 57 of Fe54), and these are uniformly mixed and dispersed to form a fine metal powder mixture 59 (foam metal molding material). The metal fine powder mixture producing step S4 of adding a predetermined pore forming material 58 to the metal fine powder mixture 59 and the metal fine powder mixture 59 produced by the metal fine powder mixture producing step S4 are formed into a thin plate (metal powder extrusion molding). Or metal powder injection molding) to form a metal fine powder molded product 59 (foamed metal molded product), and a metal fine powder molded product 59 produced by the metal fine powder molded product manufacturing step S5. The thin plate-shaped anode 11 (air electrode 38) and cathode 12 (fuel electrode 37) having a microporous structure in which a large number of fine pores 23 are formed by degreasing and sintering the metal fine powder molded product 59 at a predetermined temperature. Since the anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) are manufactured by the respective steps of the microporous structure thin plate electrode forming step S6 for manufacturing the above, the thickness dimension L1 is 0.03 mm to 1 in the steps S1 to S6. In the range of 0.5 mm (preferably in the range of 0.05 mm to 1.0 mm) It is possible to manufacture the anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) (microporous structure thin plate electrode) in which a large number of fine pores 23 (passage holes) are formed, and the anode 11 (air electrode 38). Also, the cathode 11 (fuel electrode 37) can be manufactured at a low cost, and the anode 11 contains a small amount of platinum group metal, which has an excellent catalytic activity (catalytic action) and can sufficiently and surely utilize the catalytic function. (Air electrode 38) and cathode 12 (fuel electrode 37) can be made.

The electrode manufacturing method includes a positive electrode 11 (air electrode 38) and a negative electrode 12 (fuel electrode 37) containing a small amount of platinum group metal, which has an excellent catalytic activity (catalytic action) and can sufficiently and reliably utilize the catalytic function. ), and can be suitably used for the electrolyzer 10 (hydrogen gas generation system 27) and the polymer electrolyte fuel cell 36. The anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37). Can be made. In the electrode manufacturing method, the anode 11 (air electrode 38) and the cathode 12 (fuel electrode 37) produced by steps S1 to S6 exhibit substantially the same catalytic activity (catalytic action) as the platinum group metal-supported electrode. In addition, the electrolysis device 10 can efficiently perform electrolysis, and the anode 11 and the cathode 12 that can generate a large amount of hydrogen gas in a short time can be formed, and the solid polymer fuel cell 36 is sufficient. An air electrode 38 and a fuel electrode 37 containing a small amount of platinum group metal capable of generating various electricity and supplying sufficient electric energy to a load 48 connected to the polymer electrolyte fuel cell 36. Can be made.

10 Electrolyzer 11 Anode (electrode)
12 Cathode (electrode)
13 Solid Polymer Electrolyte Membrane 14 Anode Power Feeding Member 15 Cathode Power Feeding Member 16 Anode Water Storage Tank 17 Cathode Water Storage Tank 18 Anode Main Electrode 19 Cathode Main Electrode 20 Membrane/Electrode Assembly 21 Front Surface 22 Rear Surface 23 Pore (Continuous and independent passage hole )
24 Microporous Thin Plate Electrode 25 Flow Port 26 Outer Edge 27 Hydrogen Gas Generation System 28 DC Power Supply 29 Water Storage Tank 30 Water Supply Pump 31 Oxygen Gas Liquid Separator 32 Circulation Pump 33 Circulation Pump 34 Hydrogen Gas Liquid Separator 35 Cylinder 36 Polymer electrolyte fuel cell 37 Fuel electrode 38 Air electrode 39 Solid polymer electrolyte membrane 40 Separator 41 Separator 42 Membrane/electrode assembly 43 Gas diffusion layer 44 Gas diffusion layer 45 Gas seal 46 Gas seal 47 Conductive wire 48 Load 49 Platinum group metal 50 transition metal 51 binder 52 Pt (platinum)
53 Ni (nickel)
54 Fe (iron)
55 Pt (platinum) fine powder (platinum group metal fine powder)
56 Ni (nickel) fine powder (transition metal fine powder)
57 Fe (iron) fine powder (transition metal fine powder)
58 Pore forming material (foaming agent)
59 Metal fine powder mixture 60 Metal fine powder molded product L1 Thickness dimension S1 Metal selection process S2 Metal fine powder preparation process S3 Fine powder weight ratio determination process S4 Metal fine powder mixture preparation process S5 Metal fine powder molded product production process S6 Microporous structure Thin plate electrode making process

Claims (9)

An anode and a cathode, and an electrode assembly film that is located between the anode and the cathode and joins the electrodes,
The anode and the cathode are formed from a small amount of at least one platinum group metal selected from various platinum group metals and at least two types of transition metals selected from various transition metals,
The anode and the cathode are a platinum group metal fine powder obtained by finely grinding the selected at least one platinum group metal, a transition metal fine powder obtained by finely grinding the selected at least two types of transition metals, and a predetermined binder. Add a predetermined pore-forming material to the metal fine powder mixture in which and are uniformly mixed and dispersed, and mold the metal fine-powder mixture to which the pore-forming material is added into a thin plate shape with a predetermined area, into a thin plate shape with the predetermined area. A thin plate electrode with a microporous structure in which a large number of fine pores are formed by degreasing and sintering the formed metal fine powder molded product,
Characteristically, a predetermined aqueous solution is chemically decomposed by supplying electricity to the anode and the cathode formed in the shape of a microporous thin plate to cause an oxidation reaction at the anode and a reduction reaction at the cathode. Electrolyzer. In the anode and the cathode, at least two kinds of transition metals are selected from the various transition metals so that the composite work function of the work functions of the selected at least two kinds of transition metals approximates to the work function of the platinum group metal. The electrolyzer according to claim 1, wherein a metal is selected. The electrolyzer according to claim 1 or 2, wherein an average diameter of pores formed in the anode and the cathode is in a range of 1 to 100 µm. The electrolyzer according to any one of claims 1 to 3, wherein the thickness of the anode and the thickness of the cathode are in the range of 0.03 mm to 1.5 mm. The platinum group metal is Pt (platinum), the transition metal is Ni (nickel) and Fe (iron), the work function of Ni and the work function of Fe in the anode and the cathode Ratio of the platinum group metal fine powder of Pt to the total weight of the metal fine powder mixture and the metal powder of the transition metal fine powder of Ni such that the synthetic work function of Pt is close to the work function of the platinum group metal. The electrolysis apparatus according to any one of claims 1 to 4, wherein a weight ratio to the total weight of the body mixture and a weight ratio of the transition metal fine powder of Fe to the total weight of the fine metal powder mixture are defined. The weight ratio of the Pt platinum group metal fine powder to the total weight of the metal fine powder mixture is in the range of 4 to 10%, and the weight ratio of the Ni transition metal fine powder to the total weight of the metal fine powder mixture is The electrolyzer according to claim 5, wherein the weight ratio of the transition metal fine powder of Fe to the total weight of the fine metal powder mixture is in the range of 45% to 48%, and in the range of 45% to 48%. The electrolyzer according to any one of claims 1 to 6, wherein the porosity of the anode and the cathode formed into a thin plate shape of the microporous structure is in the range of 70% to 85%. Electrolysis according to the micro density of the anode and the cathode is formed into a thin plate of a porous structure, any claims 1 to 7 in the range of 6.0g ^/ cm ² ~8.0g / cm 2 apparatus. 9. The electrolyzer according to claim 1, wherein the particle size of the platinum group metal fine powder of the platinum group metal and the particle size of the transition metal fine powder of the transition metal are in the range of 1 μm to 100 μm. ..

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