JP2020164933A - Electrolysis apparatus - Google Patents

Abstract

To provide an electrolysis apparatus including an anode and a cathode with catalytic activity (catalytic action) without using platinum group metals.SOLUTION: An anode 11 and a cathode 12, which are used for an electrolysis apparatus 10 and have catalytic activity almost the same as an anode and cathode including platinum group metals, are thin-plate foamed metal electrodes having a micro-porous structure in which: a prescribed pore-forming material is uniformly mixed and dispersed while a prescribed binder is uniformly added to mix and disperse into a permalloy fine powder obtained by pulverizing an Fe-Ni permalloy; the permalloy fine powder mixture obtained by mixing the permalloy fine powder with the binder and pore-forming material is formed like a thin plate having a prescribed area; and numbers of fine continuous pores are evenly formed while the permalloy fine powder is melted and bonded by defatting and sintering the permalloy fine powder-mixed moldings formed into the thin plate having the prescribed area.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 housed in the reaction tube, and a tubular body having a fluid inlet and a fluid outlet are provided, and the fluid inlet and the fluid outlet communicate with each other through the inside of the tubular body as a flow path, and the reaction tube. Is placed in the flow path, the catalyst is inserted into the reaction tube in a direction that makes the axis parallel to the longitudinal direction of the reaction tube, and the catalyst contains a substrate extending along a certain axis and a dehydrogenation catalyst. It is provided with a dehydrogenation catalyst layer, includes a plate-shaped portion extending along the axis while twisting in the direction in which the base material rotates 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).

Japanese Unexamined Patent Publication No. 2016-55251

The catalyst body of the hydrogen generator disclosed in Patent Document 1 includes a step of anodizing the surface of a metal molded body to form a metal oxide film containing a metal oxide, and a dehydrogenation catalyst on the metal oxide film. It is made from the process of supporting. In the step of supporting the dehydrogenation catalyst on the metal oxide film, hexachloroplatinic (IV) acid ions are formed on the metal oxide film by contacting an acidic platinum chloride aqueous solution containing hexachloroplatinum (IV) acid ions with the metal oxide film. Is attached, and the metal oxide film to which hexachloroplatinic acid (IV) acid ion is attached is fired to support platinum on the metal oxide film as a dehydrogenating catalyst.

Various platinum-supported carbons are widely used as electrodes of electrolyzers. However, since platinum group elements are precious metals and are rare resources whose production amount is limited, it is required to reduce the amount used. Further, for the widespread use of electrolyzers in the future, it is required to develop an inexpensive electrode having a non-platinum catalyst using an expensive metal other than platinum.

An object of the present invention is to provide an anode and a cathode having catalytic activity (catalytic action) without using a platinum group element, and electrolysis can be efficiently performed using a non-platinum anode and a cathode for a short time. It is an object of the present invention to provide an electrolyzer capable of generating a large amount of hydrogen gas.

A feature of the electrolysis apparatus of the present invention for solving the above problems is that the anode and the cathode are provided with an electrode joint film located between the anode and the cathode and joining the electrodes, and the anode and the cathode are provided. Permalloy fine powder obtained by uniformly mixing and dispersing a predetermined binder in permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy and uniformly mixing and dispersing a predetermined pore-forming material, and mixing a binder and a pore-forming material in the permalloy fine powder. After molding the body mixture into a thin plate with a predetermined area, the permalloy fine powder mixed molded product molded into a thin plate with a predetermined area is degreased and sintered, so that the permalloy fine powder is melt-bonded and a large number of fine continuous pores are formed. Is a thin plate-shaped foamed metal electrode having a microporous structure, and the open cells are surrounded by a permalloy melt in which permalloy fine powder is melt-bonded, and the anode and cathode, which are thin plate-shaped foamed metal electrodes having a microporous structure, are formed. It has almost the same catalytic activity as the anode and cathode containing platinum group elements, and electricity is applied to the anode and cathode, which are thin plate foam metal electrodes with a microporous structure, causing an oxidation reaction at the anode and a reduction reaction at the cathode. By raising it, a predetermined aqueous solution is chemically decomposed.

As an example of the electrolyzer of the present invention, in the electrolyzer, the work function of the permalloy fine powder used to form the anode and the cathode is similar to the work function of the platinum group element, so that Fe in Fe-Ni permalloy The content rate and the content rate of Ni in Fe-Ni permalloy have been determined.

As another example of the electrolyzer of the present invention, open cells formed on the thin plate-shaped foamed metal electrode extend between the front surface and the rear surface of the thin plate-shaped foamed metal electrode while irregularly bending in the thickness direction. At the same time, it extends between the outer peripheral edge and the inner peripheral edge of the thin plate-shaped foamed metal electrode while being irregularly bent in the radial direction.

As another example of the electrolyzer of the present invention, those open cells extending in the radial direction and bent in the thickness direction are partially connected in the radial direction to form one open cell and the other open bubble. These open cells that communicate with each other and extend radially adjacent to each other in the thickness direction are partially connected in the thickness direction so that one open cell and the other open cell communicate with each other, and the average of the open cells. The diameter is not uniform in the thickness direction and changes irregularly in the thickness direction, and is not uniform in the radial direction and changes irregularly in the radial direction.

As another example of the electrolyzer of the present invention, the average diameter of continuous pores formed in the thin plate-shaped foamed metal electrode is in the range of 1 μm to 100 μm and in the range of ± 0.1 μm to ± 5 microμm. It's changing.

As another example of the electrolyzer of the present invention, the thickness dimension of the thin plate-shaped foamed metal electrode is in the range of 0.05 mm to 0.5 mm.

As another example of the electrolyzer of the present invention, the Fe content in Fe-Ni permalloy is in the range of 45% to 55%, and the Ni content in Fe-Ni permalloy is 45% to 55%. Is in the range of.

As another example of the electrolyzer of the present invention, the porosity of open cells formed on the thin plate-shaped foamed metal electrode is in the range of 45% to 55%.

As another example of the electrolytic apparatus of the present invention, the density of the thin foamed metal electrode ^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 permalloy fine powder is in the range of 1 μm to 100 μm.

According to the electrolyzer according to the present invention, the anode and cathode used therein uniformly mix and disperse a predetermined binder in permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy, and uniformly mix and disperse a predetermined pore-forming material. A permalloy fine powder mixture obtained by mixing and dispersing and mixing a binder and a pore-forming material with a permalloy fine powder is formed into a thin plate having a predetermined area, and then the permalloy fine powder mixed molded product formed into a thin plate having a predetermined area is degreased and baked. It is a thin plate-shaped foamed metal electrode with a microporous structure in which a large number of fine continuous pores are evenly formed while the permalloy fine powder is melt-bonded by binding, and has substantially the same catalytic activity as an anode and a cathode containing a platinum group element. The anode and cathode have excellent catalytic activity (catalytic action), and the anode and cathode exhibit excellent catalytic activity (catalytic action), so that the non-platinum anode and cathode containing no platinum group element are present. Can be used to efficiently perform electrolysis, and a large amount of hydrogen gas can be generated in a short time. In the electrolyzer, the anode and cathode are made of Fe-Ni permalloy as a raw material, expensive platinum group elements are not used, and the anode and cathode are non-platinum electrodes containing no platinum group elements, so that the anode is inexpensive. By providing the cathode and the cathode, the electrolyzer can be manufactured at low cost.

Fe content in Fe-Ni permaloy and Ni content in Fe-Ni permaloy so that the work function of the permalloy fine powder used to form the anode and cathode used in the electrolyzer is similar to the work function of platinum group elements. In the electrolyzer that has been determined to be, the Fe content and Ni content in Fe-Ni permalloy are determined so that the working function of the permalloy fine powder is close to the working function of the platinum group element. Therefore, the anode and cathode have substantially the same work function as the anode and cathode containing platinum group elements, and the anode and cathode have substantially the same excellent catalytic activity (cathodic action) as the anode and cathode containing platinum group elements. , The anode and cathode can exhibit almost the same catalytic activity (cathodic action) as the anode and cathode containing platinum group elements, and electrolysis can be efficiently performed using the non-platinum anode and cathode. , A large amount of hydrogen gas can be generated in a short time.

The open cells formed on the thin plate-shaped foamed metal electrode extend between the front surface and the rear surface of the thin plate-shaped foamed metal electrode while being irregularly bent in the thickness direction, and the outer and inner peripheral edges of the thin plate-shaped foamed metal electrode. In the electrolyzer that extends while bending irregularly in the radial direction, the anode and cathode have a plurality of continuous pores that extend irregularly in the thickness direction and the radial direction. And the specific surface area of the cathode is large, and the liquid (water) can flow through these continuous pores while allowing the liquid to come into contact with the contact surfaces of the continuous pores of the anode and the cathode in a wide range, and the catalytic activity (catalytic action) of the anode and the cathode. ) Can be used effectively and to the maximum extent. Since the electrolyzer has a large specific surface area of the anode and cathode used for it and exhibits almost the same catalytic activity (catalytic action) as the anode and cathode containing platinum group elements, a non-platinum anode and cathode are used. In addition to being able to efficiently perform electrolysis, it is possible to generate a large amount of hydrogen gas in a short time.

These open cells that are adjacent in the radial direction and extend by bending in the thickness direction are partially connected in the radial direction, and one open cell and the other open bubble communicate with each other, and are adjacent in the thickness direction and bend in the radial direction. The open cells extending in the thickness direction are partially connected in the thickness direction, and one open cell and the other open cell communicate with each other, and the average diameter of the open cells is not uniform in the thickness direction but in the thickness direction. In an electrolyzer that changes irregularly toward and is not uniform in the radial direction and changes irregularly in the radial direction, one open cell and the other open cell are mutually exclusive. Since the average diameter of the open cells changes irregularly in the thickness direction and the radial direction, the specific surface areas of the anode and the cathode can be increased, and the liquid (water) passes through the continuous pores. The liquid can be brought into contact with the contact surfaces of the continuous pores of the anode and the cathode in a wide range while flowing, and the catalytic activity (catalytic action) of the anode and the cathode can be effectively and maximized. The electrolyzer uses non-platinum anodes and cathodes because the specific surface areas of the anodes and cathodes used for them are large and they exhibit excellent catalytic activity (catalytic action) similar to those of anodes and cathodes containing platinum group elements. Therefore, electrolysis can be efficiently performed, and a large amount of hydrogen gas can be generated in a short time.

Electrolyzers in which the average diameter of continuous pores formed in the thin plate foam metal electrode is in the range of 1 μm to 100 μm and changes in the range of ± 0.1 μm to ± 5 microμm are formed in the anode and cathode. Since the average diameter of the continuous pores formed is in the above range and the average diameter of the continuous pores changes in the above range, a large number of continuous pores are formed per unit volume of the anode and the cathode, and the specific surface area of the anode and the cathode is formed. Is large, and the liquid (water) can flow through these continuous pores while allowing the liquid to come into contact with the contact surfaces of the continuous pores of the anode and the cathode in a wide range, and the catalytic activity (catalytic action) of the anode and the cathode is effective and maximum. It can be used only for a limited time. Since the electrolyzer has a large specific surface area of the anode and cathode used for it and exhibits almost the same catalytic activity (catalytic action) as the anode and cathode containing platinum group elements, a non-platinum anode and cathode are used. In addition to being able to efficiently perform electrolysis, it is possible to generate a large amount of hydrogen gas in a short time.

An electrolyzer whose thickness dimension of the thin plate-shaped foamed metal electrode is in the range of 0.05 mm to 0.5 mm reduces the electrical resistance of the anode and the cathode by setting the thickness dimension of the anode and the cathode used therein in the above range. The current can be smoothly passed through the anode and the cathode. In the electrolyzer, the anode and cathode used for the electrolyzer have excellent catalytic activity (catalytic action) similar to that of the anode and cathode containing platinum group elements, and the current flows smoothly through the anode and cathode. In addition to being able to efficiently perform electrolysis in the electrolysis apparatus using the above, it is possible to generate a large amount of hydrogen gas in a short time.

An electrolyzer in which the Fe content in Fe-Ni permalloy is in the range of 45% to 55% and the Ni content in Fe-Ni permalloy is in the range of 45% to 55% is the work function of permalloy fine powder. Since the content of Fe and the content of Ni in Fe-Ni permalloy are determined in the above range so that is close to the work function of platinum group elements, the anode and cathode are anodes and cathodes containing white metal elements. It has almost the same work function as, and the anode and cathode can exhibit excellent catalytic activity (cathodic action) almost the same as the anode and cathode containing platinum group, and the electrolyzer using the anode and cathode. In addition to being able to efficiently perform electrolysis, a large amount of hydrogen gas can be generated in a short time.

An electrolysis device having a porosity of open cells formed on a thin plate foam metal electrode in the range of 45% to 55% sets the porosity of the thin plate foam metal electrode (anode and cathode) used therein in the above range. As a result, the anode and the cathode are formed into a porosity having a large number of fine continuous pores (a microporous structure in which fine continuous pores having an average diameter of 1 μm to 100 μm are formed evenly and uniformly), and the specific surface area of the anode and the cathode is formed. It is possible to make the liquid (water) pass through these continuous pores and bring the liquid into contact with the contact surfaces of the anode and the cathode in a wide range, and the anode and the cathode are with the anode and the cathode containing a platinum group metal. It is possible to reliably exert substantially the same catalytic activity (catalytic action). The electrolyzer can fully and surely utilize the catalytic functions of the anode and the cathode used therein, and can efficiently perform electrolysis in the electrolyzer using the anode and the cathode, and is short. A large amount of hydrogen gas can be generated in time.

Electrolyzer density of thin foamed metal electrode is in the range of 6.0g ^/ cm ² ~8.0g / cm 2, the density of the thin foamed metal electrodes (anode and cathode) for use therewith in the range As a result, the anode and cathode are formed into a porous structure having a large number of fine continuous pores (a microporous structure in which fine continuous pores having an average diameter of 1 μm to 100 μm are uniformly and uniformly formed), and the specific surface area of the anode and the cathode is formed. It is possible to make the liquid (water) pass through the continuous pores and bring the liquid into wide contact with the contact surfaces of the anode and the cathode in the continuous pores, and the anode and the cathode contain a white metal element. It is possible to reliably exhibit catalytic activity (catalytic action) substantially similar to that of an anode or a cathode. The electrolyzer can fully and surely utilize the catalytic functions of the anode and the cathode used therein, and can efficiently perform electrolysis in the electrolyzer using the anode and the cathode, and is short. A large amount of hydrogen gas can be generated in time.

An electrolysis device having a permalloy fine powder in the range of 1 μm to 100 μm has a large number of fine anodes and cathodes by setting the particle size of the permalloy fine powder used for forming the anode and cathode in the above range. It is formed into a porous structure with continuous pores (a microporous structure in which fine continuous pores with an average diameter of 1 μm to 100 μm are evenly and uniformly formed), and the specific surface areas of the anode and cathode can be increased, and these continuous pores can be formed. While the liquid (water) is flowing, the liquid can be brought into contact with the contact surfaces of the anode and the cathode in their continuous pores in a wide range, and the anode and the cathode have substantially the same catalytic activity (catalyst) as the anode and the cathode containing a white metal element. Action) can be reliably exerted. The electrolyzer can fully and surely utilize the catalytic functions of the anode and the cathode used therein, and can efficiently perform electrolysis in the electrolyzer using the anode and the cathode, and is short. A large amount of hydrogen gas can be generated in time.

A side view of an electrolyzer shown as an example. The perspective view of the anode and the cathode shown as an example. A partially enlarged view showing an anode and a cathode as an example. The figure explaining an example of electrolysis using an electrolysis apparatus. The figure which shows an example of the hydrogen gas generation system using an electrolyzer. 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. The figure explaining the manufacturing method of an anode and a cathode.

The details of the method for manufacturing the anode and the cathode used in the electrolyzer and the electrolyzer according to the present invention will be described with reference to the attached drawings such as FIG. 1 which is a side view of the electrolyzer 10 shown as an example. It is as follows. Note that FIG. 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 an arrow X, and the radial direction is indicated by an arrow Y.

The electrolysis device 10 (hydrogen gas generator) is a solid polymer electrolyte film 13 (electrode junction film) located (intervened) between the anode 11 (anode), the cathode 12 (cathode), and the anode 11 and the cathode 12. ) (Fluorine-based ion exchange film having a sulfonic acid group), the anode feeding member 14, the cathode feeding member 15, the anode water storage tank 16 and the cathode water storage tank 17, and the anode main electrode 18 and the cathode main electrode 19. It is formed.

The electrolyzer 10 chemically decomposes a predetermined aqueous solution by energizing the anode 11 and the cathode 12 to cause an oxidation reaction at the anode 11 and a reduction reaction at the cathode 12. In the electrolysis apparatus 10, the anode 11, the cathode 12, and the solid polymer electrolyte membrane 13 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly (MEA), and the membrane / electrode assembly 20 is formed. Is sandwiched between the anode feeding member 14 and the cathode feeding member 15. The solid polymer electrolyte membrane 13 has proton conductivity and no electron conductivity.

The anode feeding member 14 is located outside the anode 11 and is in close contact with the anode 11 to supply a positive current to the anode 11. The water storage tank 16 for the anode is located outside the anode feeding member 14 and is in close contact with the anode 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 feeding member 14. The cathode feeding member 15 is located outside the cathode 12 and is in close contact with the cathode 12, and feeds a negative current to the cathode 12. The cathode water storage tank 17 is located outside the cathode feeding member 15 and is in close contact with the cathode feeding member 15. The cathode main electrode 19 is located outside the water storage tank 17 for the cathode and supplies a negative current to the cathode feeding 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, a predetermined area and a predetermined thickness dimension L1, and the planar shape thereof is formed into a quadrangle. ing. The anode 11 and the cathode 12 are porous (microporous structure) thin plate-shaped foamed metal electrodes 24 having a large number of fine continuous pores 23 (continuous ventilation holes). An aqueous solution (liquid) flows through the continuous pores 23 (continuous ventilation holes). The planar shapes of the anode 11 and the cathode 12 are not particularly limited, and can be formed into any other planar shape such as a circular shape or an elliptical shape according to the intended use, in addition to the quadrangular shape.

The anode 11 and the cathode 12 (thin plate-shaped foamed metal electrode 24 having a microporous structure) are formed of Fe-Ni permalloy 49 that has been finely pulverized (pulverized) into powder. A predetermined binder 51 (powdered resin-based binder) is mixed with the permalloy fine powder 50 (Fe-Ni permalloy 49 processed into fine powder) of Fe-Ni permalloy 49, and the permalloy fine powder 50 and the binder 51 are made uniform. A permalloy fine powder mixture 53 mixed and dispersed in the permalloy fine powder mixture 53 was further mixed with a predetermined pore-forming material 52 (foaming agent), and the pore-forming material 52 was uniformly mixed and dispersed in the fine powder mixture 53. make. The prepared Permalloy fine powder mixture 53 is formed into a thin plate having a predetermined area by extrusion molding or injection molding (extrusion molding or injection molding) to prepare a thin plate-shaped Permalloy fine powder mixed molded product 54, and the prepared fine powder mixed molded product. The anode 11 and the cathode 12 are made by degreasing and sintering (baking) 54 at a predetermined temperature (see FIG. 9). The open cells 25 are defined and surrounded by a permalloy melt in which the permalloy fine powder 50 is melt-bonded.

At the anode 11 and the cathode 12, Fe (relative to the total weight (100%) of Fe-Ni permalloy 49) in Fe-Ni permalloy 49 so that the work function of the permalloy fine powder 50 approximates the work function of the platinum group element. The iron) content (weight ratio) and the Ni (nickel) content (weight ratio) have been determined. Specifically, the Fe content (weight ratio) in Fe-Ni permalloy 49 is in the range of 45% to 55%, preferably 49% to 51%, and the content of Ni in Fe-Ni permalloy 49. The rate (weight ratio) is in the range of 45% to 55%, preferably in the range of 49% to 51%.

The work function of Fe is 4.67 (eV), and the work function of Ni is 5.22 (eV). When the Fe content to the total weight of Fe-Ni permalloy 49 and the Ni content to the total weight of Fe-Ni permalloy 49 are out of the above range, the working function of the permalloy fine powder 50 is approximated to the working function of the platinum group element. The anode 11 and the cathode 12 produced by degreasing and sintering (baking) the permalloy fine powder mixed molded product 54 obtained by molding the permalloy fine powder mixed mixture 53 could contain (support) a platinum group element. It cannot exhibit almost the same catalytic activity (catalytic action) as that of iron and nickel.

In the polymer electrolyte fuel cell 10, the Fe content and the Ni content in the Fe—Ni permalloy 49 are in the above range so that the working function of the permalloy fine powder 50 is close to the working function of the platinum group element. Therefore, the anode 11 and the cathode 12 have substantially the same work function as the anode and the cathode containing (supporting) the platinum group, and the anode 11 and the cathode 12 have substantially the same excellent catalyst as the anode and the cathode containing the platinum group. It can exert its activity (cathodic action).

A large number of fine continuous pores 23 (continuous ventilation holes) having different diameters are formed in the anode 11 and the cathode 12 (thin plate-shaped foamed metal electrode 24 having a microporous structure). Since the anode 11 and the cathode 12 are formed with a large number of fine continuous pores 23 (continuous ventilation holes), their specific surface areas are large. The continuous pores 23 formed in the anode 11 and the cathode 12 have a plurality of passage ports 25 opened in the front surface 21 of the anode 11 and the cathode 12, and a plurality of passage ports opened in the rear surface 22 of the anode 11 and the cathode 12. 25, which penetrates the anode 11 and the cathode 12 in the thickness direction from the front surface 21 of the anode 11 and the cathode 12 toward the rear surface 22, and from the center of the anode 11 and the cathode 12 toward the outer peripheral edge 26. It penetrates in its radial direction.

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

The average diameter (opening area) of these continuous pores 23 is not uniform in the thickness direction and changes irregularly in the thickness direction, and is not uniform in the radial direction and is in the radial direction. It is changing irregularly toward. The continuous pores 23 are irregularly opened in the thickness direction and the radial direction while the average diameter (opening area) is increasing or decreasing. Further, the average diameter (opening area) of the air passage port 25 opened in the front surface 21 of the anode 11 and the cathode 12 and the air flow port 25 opened in the rear surface 22 are not uniform, and the average diameters are all different. ing. The average diameter (opening area) of the continuous pores 23 and the average diameter (opening area) of the passage ports 25 of the front and rear surfaces 21 and 22 are in the range of 1 μm to 100 μm, preferably in the range of 45 μm to 55 μm, ± 0. It changes in the range of 1 μm to ± 5 μm (change width of the average diameter of the continuous pores 23).

In the electrolysis device 10, a plurality of continuous pores 23 (continuous ventilation holes) extending while irregularly bending in the thickness direction and the radial direction are formed in the anode 11 and the cathode 12 used therein, and the average diameter of the pores 23 is 1. Since it is in the range of ~ 100 μm (preferably in the range of 45 μm to 55 μm) and the range of change in the average diameter of the continuous pores 23 is in the range of ± 0.1 μm to ± 5 μm, per unit volume of the anode 11 and the cathode 12. A large number of continuous pores 23 are formed, and the specific surface areas of the anode 11 and the cathode 12 can be increased, and the liquid (water) flows through the pores 23 while the liquid is passed through the pores 23 of the anode 11 and the cathode 12. Can be brought into contact with a wide range, and the catalytic activity (catalytic action) of the anode 11 and the cathode 12 can be effectively and maximized.

The anode 11 and the cathode 12 (thin plate-shaped foamed metal electrode 24 having a microporous structure) have a thickness dimension L1 in the range of 0.05 mm to 0.5 mm. If the thickness dimension L1 of the anode 11 and the cathode 12 is less than 0.05 mm, 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 is changed. It may not be possible to maintain. When the thickness dimension L1 of the anode 11 and the cathode 12 exceeds 0.5 mm, the electrical resistance of the anode 11 and the cathode 12 increases, the current does not flow smoothly through the anode 11 and the cathode 12, and the anode 11 and the cathode 12 are electrolyzed. When used in the device 10, the electrolysis device 10 cannot efficiently perform electrolysis, and the electrolysis device 10 cannot generate a large amount of hydrogen gas in a short time.

Since the thickness dimension L1 of the anode 11 and the cathode 12 used in the electrolyzer 10 is in the range of 0.05 mm to 0.5 mm, the anode 11 and the cathode 12 have high strength and maintain their shapes. This makes it possible to prevent damage or damage to the anode 11 and the cathode 12 when an impact is applied to the anode 11 and the cathode 12. Further, the electrical resistance of the anode 11 and the cathode 12 can be reduced, the current flows smoothly through the anode 11 and the cathode 12, and when the anode 11 and the cathode 12 are used in the electrolyzer 10, the electrolyzer 10 The electrolysis can be performed efficiently, and a large amount of hydrogen gas can be generated in a short time in the electrolysis apparatus 10.

The anode 11 and the cathode 12 (thin plate-shaped foamed metal electrode 24 having a microporous structure) have a porosity in the range of 45% to 55%. If the porosity of the anode 11 and the cathode 12 is less than 45%, a large number of fine continuous pores 23 (continuous ventilation 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 can be increased. Can not. When the pore ratios of the anode 11 and the cathode 12 exceed 55%, the average diameter (opening area) of the continuous pores 23 (continuous ventilation holes) and the average diameter (opening area) of the passage ports 25 on the front and rear surfaces 21 and 22 are required. The anode 11 and the cathode 12 become larger than the above, and the strength of the anode 11 and the cathode 12 decreases. When an impact is applied, the anode 11 and the cathode 12 may be easily damaged or damaged, and the shape of the anode 11 and the cathode 12 may not be maintained. The catalytic activity of the anode 11 and the cathode 12 is reduced, the anode 11 and the cathode 12 cannot exhibit sufficient catalytic activity, and the catalytic activity (catalytic action) of the anode 11 and the cathode 12 cannot be effectively used.

Since the porosity of the anode 11 and the cathode 12 used in the electrolysis device 10 is within the above range, a large number of fine continuous pores 23 (having an average diameter of 1) in which the anode 11 and the cathode 12 have different average diameters (opening areas) Continuous pores in the range of ~ 100 μm, preferably in the range of 45 μm to 55 μm) and a large number of fine front and rear surfaces 21 and 22 with different average diameters (opening areas) 25 (average diameter in the range of 1 to 100 μm). , Preferably, it is formed into a porous material (microporous structure) having a passage port 25) in the range of 45 μm to 55 μm, the specific surface area of the anode 11 and the cathode 12 can be increased, and the pores 23 are made of liquid (water). ) Can flow and bring the liquid into wide contact with the contact surfaces of the anode 11 and the cathode 12 in their pores 23. Further, the catalytic action of the anode 11 and the cathode 12 is improved, the anode 11 and the cathode 12 can exhibit excellent catalytic activity, and when the anode 11 and the cathode 12 are used in the electrolyzer 10, the electrolyzer 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.

The anode 11 and cathode 12 (thin foamed metal electrode 24 of the micro-porous structure) in the range that the density of ^{6.0g / cm 2 ~8.0g / cm 2} , preferably, 6.5g ^/ cm 2 ~7. It is in the range of 5 g / cm ² . If 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 easily become when an impact is applied. In some cases, the shape of the anode 11 and the cathode 12 is reduced, and the anode 11 and the cathode 12 cannot exhibit sufficient catalytic activity, so that the anode 11 and the cathode 12 cannot maintain their shape. The catalytic activity (catalytic action) of 11 and the cathode 12 cannot be effectively utilized. When the densities of the anode 11 and the cathode 12 exceed 8.0 g / cm ² (7.5 g / cm ² ), a large number of fine continuous pores 23 and a large number of fine passage ports 25 are formed in the anode 11 and the cathode 12. Therefore, the specific surface areas of the anode 11 and the cathode 12 cannot be increased, and the catalytic action of the anode 11 and the cathode 12 is lowered, so that the anode 11 and the cathode 12 cannot exhibit sufficient catalytic activity, and the anode The catalytic activity (catalytic action) of 11 and the cathode 12 cannot be effectively utilized.

Since the densities of the anode 11 and the cathode 12 used in the electrolysis device 10 are within the above range, a large number of fine continuous pores 23 (having an average diameter of 1 to 1) in which the anode 11 and the cathode 12 have different average diameters (opening areas). Continuous pores in the range of 100 μm, preferably in the range of 45 μm to 55 μm) and a large number of fine front and rear surfaces 21 and 22 having different average diameters (opening areas) 25 (with an average diameter in the range of 1 to 100 μm). Preferably, it is formed into a porous material (microporous structure) having a passage port 25) in the range of 45 μm to 55 μm, the specific surface areas of the anode 11 and the cathode 12 can be increased, and the pores 23 are made of liquid (water). The liquid can be widely brought into contact with the contact surfaces of the anode 11 and the cathode 12 in their pores 23, and the 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, the anode 11 and the cathode 12 can exhibit excellent catalytic activity, and when the anode 11 and the cathode 12 are used in the electrolyzer 10, the electrolyzer 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.

The particle size of the permalloy fine powder 50 (Fe-Ni permalloy 49 processed into powder) is in the range of 1 μm to 100 μm, preferably in the range of 30 μm to 60 μm. If the particle size of the Permalloy fine powder 50 is less than 1 μm, the continuous pores 23 (continuous ventilation holes) are blocked by the Permalloy fine powder 50, and a large number of fine continuous pores 23 cannot be formed in the anode 11 and the cathode 12. , The specific surface areas of the anode 11 and the cathode 12 cannot be increased, and the catalytic action of the anode 11 and the cathode 12 is lowered, so that the anode 11 and the cathode 12 cannot exhibit sufficient catalytic activity, and the anode 11 and the cathode 12 The catalytic activity (catalytic action) of the cathode 12 cannot be effectively used.

When the particle size of the permalloy fine powder 50 exceeds 100 μm, the average diameter (opening area) of the continuous pores 23 and the average diameter (opening area) of the passage ports 25 on the front and rear surfaces 21 and 22 become larger than necessary, and the anode 11 In addition, a large number of fine continuous pores 23 cannot be formed in the cathode 12, the specific surface areas of the anode 11 and the cathode 12 cannot be increased, and the catalytic action of the anode 11 and the cathode 12 is reduced, so that the anode 11 and the cathode 12 and the cathode 12 have a reduced specific surface area. The cathode 12 cannot exhibit sufficient catalytic activity, and the catalytic activity (catalytic action) of the anode 11 and the cathode 12 cannot be effectively utilized.

In the electrolysis device 10, since the particle size of the permalloy fine powder 50 forming the anode 11 and the cathode 12 used therein is in the above range, the anode 11 and the cathode 12 have a large number of fine continuous particles having different average diameters (opening areas). Pore 23 (continuous pore 23 having an average diameter in the range of 1 to 100 μm, preferably 45 μm to 55 μm) and a large number of fine front and rear surfaces 21 and 22 having different average diameters (opening areas) 25 (average) It is formed into a porous material (microporous structure) having a passage port 25) having a diameter in the range of 1 to 100 μm, preferably in the range of 45 μm to 55 μm, and the specific surface areas of the anode 11 and the cathode 12 can be increased. While the liquid (water) is flowing through the pores 23, the liquid can be widely brought into contact with the contact surfaces of the anode 11 and the cathode 12 in the pores 23, and the catalytic activity (catalytic action) of the anode 11 and the cathode 12 is effective. It can be used to the maximum. 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 when the anode 11 and the cathode 12 are used in the electrolytic apparatus 10, the electrolytic apparatus 10 can efficiently perform electrolysis, and the electrolysis device 10 can generate a large amount of hydrogen gas in a short time.

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

The electrolysis of water in the electrolyzer 10, as shown by the arrows in FIG. 4, water (H 2 _O) is water in the anode reservoir 16 and the cathode reservoir 17, to the anode main electrode 18 from the power supply + Is supplied, and a negative current is supplied from the power source to the cathode main electrode 19. The positive current fed to the anode main electrode 18 is fed from the anode feeding member 14 to the anode 11 (anode), and the negative current fed to the cathode main electrode 19 is fed from the cathode feeding member 15 to the cathode 12 (cathode). Will be done.

At the anode 11 (electrode), oxygen is generated by the anode reaction (catalysis) of 2H ₂ O → 4H ⁺ + 4e ⁻ + O ₂ , and at the cathode 12 (electrode), the cathode reaction (catalysis) of 4H ⁺ + 4e ⁻ → 2H _2. ) Produces hydrogen. Protons (hydrogen ions: H ⁺ ) move from the anode 11 to the cathode 12 (electrode) through the solid polymer electrolyte membrane 13. Protons generated by the anode 11 pass through the solid polymer electrolyte membrane 12.

In the electrolysis device 10, Fe is used so that the work function of the permalloy fine powder 50 obtained by finely pulverizing the Fe—Ni permalloy 49 forming the anode 11 (electrode) and the cathode 12 (electrode) is similar to the work function of the platinum group element. -Since the Fe content (weight ratio) and Ni content (weight ratio) in Ni Permalloy 49 have been determined, the anode 11 and the cathode 12 contain (support) a platinum group element (platinum). It has substantially the same work function as the cathode, exhibits excellent catalytic activity (catalytic action) substantially similar to that of an anode or cathode containing a platinum group element (platinum), and electrolysis of water is efficiently performed.

In the electrolysis of the NaOH aqueous solution, an anode reaction (catalysis) of 4OH ⁻ → 2H ₂ O + O ₂ + 4e ⁻ occurs at the anode 11, and a cathode reaction (catalysis) of 2H ₂ O + 2e ⁻ → 2OH ⁻ + H ₂ occurs at the cathode 12. Occurs. In the electrolysis of the H ₂ SO ₄ aqueous solution, an anode reaction (catalysis) of 2H ₂ O → O ₂ + 4H ⁺ + 4e ⁻ occurs at the anode 11, and a cathode reaction (catalysis) of 2H ⁺ + 2e ⁻ → H ₂ occurs at the cathode 12. Occurs.

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

The hydrogen gas generation system 27 includes an electrolyzer 10, a DC power source 28 that supplies electricity to the anode 11 and the cathode 12 of the electrolyzer 10, a water storage tank 29 that stores water (pure water), and water (pure). A water supply pump 30 for supplying water), an oxygen gas-liquid separator 31, two circulation pumps 32 and 33 for supplying water (pure water), a hydrogen gas-liquid separator 34, and a bomb 35 for storing hydrogen (pure water). It is formed from a 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 source 28 to the electrolysis device 10, and the electrolysis device 10 performs electrolysis to decompose water into hydrogen and oxygen. Oxygen flows into the oxygen-gas-liquid separator 31 and is released into the atmosphere after gas-liquid separation. The gas-liquid separated water 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, and after gas-liquid separation, flows into the cylinder 35 (hydrogen tank). The gas-liquid separated water in the hydrogen gas-liquid separator 354 is supplied to the electrolyzer 10 again by the circulation pump 33.

In the electrolyzer 10, the anode 11 and the cathode 12 used therein uniformly mix and disperse the predetermined binder 51 into the permalloy fine powder 50 obtained by finely pulverizing Fe-Ni permalloy 49, and uniformly mix the predetermined pore-forming material 52. Permalloy fine powder mixture 53, which is a mixture of permalloy fine powder 50, binder 51 and pore-forming material 52, is formed into a thin plate with a predetermined area, and then molded into a thin plate with a predetermined area. A thin plate-shaped foamed metal electrode 24 having a microporous structure in which a large number of fine continuous pores 23 are uniformly and evenly formed while the permalloy fine powder 50 is melt-bonded by degreasing and sintering the substance 54, and is a platinum group element. Since the anode 11 and the cathode 12 have excellent catalytic activity (catalytic action), the anode 11 and the cathode 12 have excellent catalytic activity (catalytic action) because they have substantially the same catalytic activity as the anode and the cathode containing (supporting). ), The non-platinum anode 11 and cathode 12 containing no platinum group element can be used to efficiently perform electrolysis, and a large amount of hydrogen gas can be generated in a short time.

In the electrolyzer 10, the anode 11 and the cathode 12 are made of Fe-Ni permalloy 49 as a raw material, an expensive platinum group element (platinum) is not used, and the anode 11 and the cathode 12 are non-platinum containing no platinum group element. Since it is an electrode of the above, the electrolyzer can be manufactured at low cost by providing the inexpensive anode 11 and cathode 12, and the operating cost of the electrolyzer 10 can be reduced.

FIG. 6 is a side view of the polymer electrolyte fuel cell 36 using the air electrode 38 (anode 11) and the fuel electrode 37 (cathode 12), and FIG. 7 is the anode 11 (anode 38) and the cathode 12 (cathode 12). It is a figure which shows the result of the electromotive force test of a fuel electrode 37). FIG. 8 is a diagram showing the results of an 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 cathode 12 (fuel electrode 37) used in the electrolyzer 10 were used for the polymer electrolyte fuel cell 36 shown in FIG. The electromotive voltage of the load was measured, the load 48 was connected to the polymer electrolyte fuel cell 36, and its IV characteristics were measured.

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

The separators 40 and 41 are engraved (engraved) with supply channels for reaction gases (hydrogen, oxygen, etc.). 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 (MEA), and the membrane / electrode assembly 42 is separated from 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 at the upper and lower parts of the gas diffusion layer 43. Gas seals 46 are installed between the air electrode 38 and the separator 41 at the upper and lower parts of 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 ⁻ . After that, protons move from the fuel electrode 37 to the air electrode 38 through the solid polymer electrolyte membrane 39, and electrons move to the air electrode 38 through the lead wire 47. Protons generated at the fuel electrode 37 pass through the solid polymer electrolyte membrane 39. At the air electrode 38, the protons transferred from the solid polymer electrolyte membrane 39 and the electrons transferred through the lead wire 47 react with oxygen in the air, and water is generated by the reaction of 4H ⁺ + O ₂ + 4e → 2H ₂ O.

In the polymer electrolyte fuel cell 10, the work function of the permalloy fine powder 50 obtained by finely pulverizing Fe-Ni permalloy 49 forming the fuel electrode 37 (cathode 12) and the air electrode 38 (anodide 12) is the work function of the platinum group element. Since the Fe content (weight ratio) and the Ni content (weight ratio) in the Fe-Ni permalloy 49 are determined so as to be close to, the fuel electrode 37 (cathode 12) and the air electrode 38 (anode) are determined. 11) has substantially the same work function as the fuel electrode or air electrode containing (supporting) the platinum group element (platinum), and has almost the same excellent catalytic activity as the fuel electrode or air electrode containing the platinum group element (platinum). It exhibits (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 the electrodes) for 15 minutes after the hydrogen gas was injected. Was measured. In the figure showing the result of the electromotive voltage test in FIG. 7, the horizontal axis represents the measurement time (min), and the vertical axis represents the electrode (fuel electrode 37 or air electrode 38) and the electrode (fuel electrode 37 or air electrode 38). Represents the voltage (V) between (between electrodes). In the polymer electrolyte fuel cell using the electrode (platinum electrode) using (supporting) the platinum group element, the voltage between the electrodes is 1.079 (as can be seen from FIG. 7 showing the result of the electromotive voltage test). V) It was around. On the other hand, in the polymer electrolyte fuel cell 36 using non-platinum electrodes (fuel electrode 37 and air electrode 38), the electrode (fuel electrode 37 and air electrode 38) and the electrode (fuel electrode 37 and air electrode 38) are The voltage (electromotive force) between (between electrodes) was 0.98 (V) to 1.02 (V).

In the IV characteristic test, a load 48 is connected between the electrodes (fuel electrode 37 and air electrode 38) and the electrodes (fuel electrode 37 and air electrode 38) (between the electrodes), and the relationship between voltage and current is measured. did. In the figure showing the result of the IV characteristic test of FIG. 8, the horizontal axis represents the current (A) and the vertical axis represents the voltage (V). In the polymer electrolyte fuel cell 36 using the fuel electrode 37 (non-platinum electrode) and the air electrode 38 (non-platinum electrode), as can be seen from FIG. 8 showing the results of the IV characteristic test, a platinum group element is used. The results were not much different from the voltage drop rate of the polymer electrolyte fuel cell using the (supported) electrode (platinum electrode). As shown in the result of the electromotive voltage test of FIG. 7 and the result of the IV characteristic test of FIG. 8, the non-platinum fuel electrode 37 (cathode 12) and the air electrode 38 (anode 11) that do not use platinum group elements are used. It was confirmed that has an excellent catalytic action that promotes the reaction of releasing electrons to become hydrogen ions, and also has an oxygen reduction function (catalytic action) that is substantially the same as that of an electrode using platinum.

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 (electrode) and the cathode 12 (electrode) have a content rate determination step S1, a permalloy fine powder preparation step S2, a permalloy fine powder mixture preparation step S3, and a permalloy fine powder mixed molded product preparation step S4. , It is manufactured by an electrode manufacturing method having a thin plate-shaped foamed metal electrode manufacturing step S5. In the electrode manufacturing method, the anode 11 and the cathode 12 are manufactured using Fe—Ni permalloy 49 as a raw material.

In the content rate determination step S1, Fe (iron) with respect to the total weight of Fe-Ni permalloy 49 so that the work function of the permalloy fine powder 50 obtained by finely pulverizing Fe-Ni permalloy 49 is close to the work function of the platinum group element. The content rate and the Ni (nickel) content rate are determined. The Fe content in Fe-Ni permalloy 49 is determined in the range of 45% to 55%, preferably 49% to 51%, and the Ni content in Fe-Ni permalloy 49 is 45% to 55. It is determined in the range of%, preferably in the range of 49% to 51%.

In the permalloy fine powder preparation step S2, Fe—Ni permalloy 49 formed from Fe and Ni having a content determined by the content rate determination step is finely pulverized to prepare a permalloy fine powder 50. Fe-Ni permalloy 49 is finely pulverized by a fine pulverizer to a particle size of 1 μm to 100 μm, preferably 30 μm to 60 μm, and a permalloy fine powder having a particle size of 1 μm to 100 μm, preferably 30 μm to 60 μm. Make a body 50.

The electrode manufacturing method is a porosity having a large number of fine continuous pores 25 (continuous ventilation holes) by finely pulverizing Fe-Ni Permalloy 49 to a particle size of 1 μm to 100 μm, preferably 30 μm to 60 μm. The anode 11 and the cathode 12 (thin plate-shaped foamed metal electrode 24) having a microporous structure having a large specific surface area can be formed, and the liquid (water) flows through the continuous pores 23 while the liquid is passed through the anode 11 and the cathode. An anode 11 and a cathode 12 can be made that can be extensively contacted with the contact surfaces of those pores 23 of 12.

In the permalloy fine powder mixture preparation step S3, a predetermined binder 51 and a predetermined pore forming material 52 (foaming agent) are added to the permalloy fine powder 50 prepared in the permalloy fine powder preparation step S2, and the binder 51 and pores are added to the permalloy fine powder 50. The permalloy fine powder mixture 53 is prepared by uniformly mixing and dispersing the forming material 52. Since an expensive platinum group metal (platinum (Pt)) is not used in the electrode manufacturing method, the anode 11 and the cathode 12 can be manufactured at low cost.

In the permalloy fine powder mixture preparation step S3, the permalloy fine powder 50 of Fe-Ni permalloy 49 and the binder 51 (powder-based resin binder) are put into a mixer or agitator, and the Fe-Ni permalloy 49 is added by the mixer or agitator. Permalloy fine powder 50 and the binder 51 are stirred and mixed to prepare a permalloy fine powder mixture 53 (foam metal molding material) in which the permalloy fine powder 50 and the binder 51 are uniformly mixed and dispersed. Next, a predetermined amount of the pore-forming material 52 (powder foaming agent) is mixed (added) into the permalloy fine powder mixture 53. A predetermined amount of the pore-forming material 52 is put into a mixer or a stirrer, and the permalloy fine powder mixture 52 (foam metal molding material) in which the pore-forming material 52 is uniformly mixed and dispersed in the permalloy fine powder mixture 53 by the mixer or the stirrer. make. The average diameter and porosity of the continuous pores 23 formed in the anode 11 and the cathode 12 are determined by the amount (addition amount) of the pore-forming material 52 (powder foaming agent) mixed in.

In the Permalloy fine powder mixture preparation step S4, the Permalloy fine powder mixture 53 (foam metal molding material) prepared in the Permalloy fine powder mixture preparation step S3 is injected into an injection molding machine (not shown) or an extrusion molding machine (not shown). ), The permalloy fine powder mixture 53 is injection molded by an injection molding machine, or the permalloy fine powder mixture 53 is extruded by an extrusion molding machine, and the permalloy fine powder mixture 53 is formed into a thin plate having a predetermined area (thickness dimension L1). (In the range of 0.05 mm to 0.5 mm), a permalloy fine powder mixed molded product 54 (foamed metal molded product) is prepared.

In the thin plate-shaped foamed metal electrode producing step S5, the permalloy fine powder mixed molded product 54 (foamed metal molded product) produced by the injection molding or extrusion molding of the permalloy fine powder mixed molded product preparation step S4 is degreased and degreased. The body-mixed molded product 54 is put into a firing furnace (combustion furnace, electric furnace, etc.), and the permalloy fine powder mixed molded product 54 is sintered (baked) at a predetermined temperature for a predetermined time in the firing furnace to obtain a large number of fine continuous pores 23. (Continuous ventilation holes) are formed evenly and uniformly, and the anode 11 and cathode 12 (thickness dimension L1 is 0) of a microporous structure defined and surrounded by the permalloy melt of the permalloy fine powder 50 in which the open cells 23 are melt-bonded. Make an anode 11 and a cathode 12) of .05 mm to 0.5 mm.

The sintering (baking) temperature is 900 ° C to 1400 ° C. The sintering (baking) time is 2 hours to 6 hours. In the thin plate-shaped foamed metal electrode producing step S5, when the permalloy fine powder mixed molded product 54 (foamed metal molded product) formed into a thin plate having a predetermined area is sintered, the pore-forming material is inside the permalloy fine powder mixed molded product 54. After the 52 (powder foaming agent) foams, the pore forming material 52 disappears from the inside of the permalloy fine powder mixed molded product 54, and a large number of fine continuous pores 25 (continuous ventilation holes) are formed in the microporous structure. The anode 11 and the cathode 12 (the anode 11 and the cathode 12 having a thickness dimension L1 of 0.05 mm to 0.5 mm) are manufactured.

In the electrode manufacturing method, the permalloy fine powder 32 of Fe-Ni permalloy 31 is connected via a binder 33 by injection molding or extrusion molding, and the permalloy fine powder mixed molded product 36 (foam metal molding) produced by injection molding or extrusion molding. By degreasing the material) and then sintering (baking) it at a predetermined temperature, an anode 11 and a cathode 12 having a microporous structure having a large number of fine continuous pores 23 (continuous ventilation holes) can be produced and are high. It is possible to make the anode 11 and the cathode 12 which have strength, can maintain the shape, and can prevent breakage or damage when an impact is applied. In the electrode manufacturing method, since the anode 11 and the cathode 12 having a thickness dimension L1 in the range of 0.05 mm to 0.5 mm can be made, the anode 11 and the cathode 12 having a small electric resistance and capable of smoothly passing an electric current can be formed. Can be made.

The electrode manufacturing method is based on the Fe content and Ni content in Fe-Ni permalloy 49 so that the work function of the permalloy fine powder 50 obtained by finely pulverizing Fe-Ni permalloy 49 is close to the work function of the platinum group element. Permalloy fine powder making step and permalloy fine powder making step to make permalloy fine powder 50 by finely pulverizing Fe-Ni permalloy 49 formed from Fe and Ni of content rate decided by content rate determination step A predetermined binder 51 and a predetermined pore-forming material 52 are added to the permalloy fine powder 50 prepared in the fine powder preparation step, and the binder 51 and the pore-forming material 52 are uniformly mixed and dispersed in the permalloy fine powder 50 to make the permalloy fine powder. Permalloy fine powder mixture preparation step of making a mixture 53 and permalloy fine powder mixture 53 prepared by a step of making a permalloy fine powder mixture are molded into a thin plate by injection molding or extrusion molding to make a permalloy fine powder mixed molded product 54. The permalloy fine powder mixed molded product 54 prepared by the body mixed molded product preparation step and the permalloy fine powder mixed molded product preparation step is degreased, and the permalloy fine powder mixed molded product 54 is sintered at a predetermined temperature to obtain the permalloy fine powder 50. A large number of fine continuous pores 23 are uniformly and uniformly formed while being melt-bonded, and a thin plate-like foam having a microporous structure in which the open cells 23 are defined and surrounded by the permalloy melt in which the permalloy fine powder 50 is melt-bonded. Since the anode 11 and the cathode 12 are manufactured by each step of the step of making the thin plate foam metal electrode 24 for making the metal electrode 24, the thickness dimension L1 is in the range of 0.05 mm to 0.5 mm in a large number by these steps S1 to S5. The anode 11 and the cathode 12 (thin plate-shaped foamed metal electrode 24 having a microporous structure) having the fine continuous pores 23 (continuous ventilation holes) formed in the above can be manufactured, and the anode 11 and the cathode 12 can be manufactured at low cost. ..

The electrode manufacturing method can exhibit excellent catalytic activity (catalytic action) substantially similar to that of an anode or cathode containing (supporting) a platinum group element, and also has excellent catalytic activity (catalytic action). Platinum group metal-free anodes 11 and 12s can be made that can fully and reliably utilize their functions. In the electrode manufacturing method, since the anode 11 and the cathode 12 produced thereby exhibit excellent catalytic activity (catalytic action) substantially similar to those of the anode and the cathode containing (supporting) platinum group elements, the electrolysis apparatus 10 is used. It is possible to produce a non-platinum anode 11 and a cathode 12 that do not contain platinum group elements, which can efficiently perform electrolysis and generate a large amount of hydrogen gas in a short time.

10 Electrolyzer 11 Anode (electrode)
12 Cathode (electrode)
13 Solid polymer electrolyte membrane 14 Anode feeding member 15 Cathode feeding member 16 Anode water storage tank 17 Cathode water storage tank 18 Anode main electrode 19 Cathode main electrode 20 Membrane / electrode junction 21 Front surface certificate 22 Rear surface 23 Continuous bubble (continuous communication) Pore)
24 Thin plate foam metal electrode with microporous structure 25 Passage port 26 Outer peripheral 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 Bomb 36 Solid polymer 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 Lead wire 48 Load 49 Fe −Ni Permalloy 50 Permalloy fine powder 51 Binder 52 Pore forming material (foaming agent)
53 Permalloy fine powder mixture 54 Permalloy fine powder mixed molded product (foamed metal molded product)
L1 Thickness dimension S1 Content rate determination process S2 Permalloy fine powder preparation process S3 Permalloy fine powder mixture production process S4 Permalloy fine powder mixed molding production process S5 Thin plate foam metal electrode production process

Claims (10)

It is provided with an anode and a cathode, and an electrode junction film located between the anode and the cathode and joining the electrodes.
The anode and the cathode uniformly mix and disperse a predetermined binder in permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy, and uniformly mix and disperse a predetermined pore-forming material, and the binder is mixed with the permalloy fine powder. The permalloy fine powder mixture mixed with the pore-forming material is formed into a thin plate having a predetermined area, and then the permalloy fine powder mixed mixture formed into a thin plate having a predetermined area is degreased and sintered to obtain the permalloy. It is a thin plate-shaped foamed metal electrode having a microporous structure in which a large number of fine continuous pores are evenly formed while the fine powder is melt-bonded. The permalloy melt in which the permalloy fine powder is melt-bonded surrounds the open cells.
The anode and the cathode, which are thin plate-shaped foamed metal electrodes having a microporous structure, have substantially the same catalytic activity as the anode and cathode containing platinum group elements, and the anode, which is a thin plate-shaped foamed metal electrode having a microporous structure. An electrolysis apparatus characterized by chemically decomposing a predetermined aqueous solution by energizing the cathode and causing an oxidation reaction at the anode and a reduction reaction at the cathode. In the electrolysis device, the content rate of Fe in the Fe—Ni permalloy and the work function of the permalloy fine powder forming the anode and the cathode used therein are similar to the work function of the platinum group element. The electrolysis apparatus according to claim 1, wherein the content of Ni in Fe-Ni permalloy is determined. The open cells formed on the thin plate-shaped foamed metal electrode extend between the front surface and the rear surface of the thin plate-shaped foamed metal electrode while being irregularly bent in the thickness direction, and are outside the thin plate-shaped foamed metal electrode. The electrolyzer according to claim 1 or 2, wherein the electrolyzer extends between the peripheral edge and the inner peripheral edge while irregularly bending in the radial direction. These open cells that are adjacent to the radial direction and bend and extend in the thickness direction are partially connected in the radial direction so that one open cell and the other open cell communicate with each other and are adjacent to each other in the thickness direction. The open cells that bend and extend in the radial direction are partially connected in the thickness direction, and one open cell and the other open cell communicate with each other, and the average diameter of the open cells is in the thickness direction. The third aspect of claim 3, which is not uniform toward the thickness and changes irregularly in the thickness direction, and is not uniform toward the radial direction and changes irregularly toward the radial direction. The electrolyzer described. The electrolysis according to claim 4, wherein the average diameter of the continuous pores formed in the thin plate-shaped foamed metal electrode is in the range of 1 μm to 100 μm and changes in the range of ± 0.1 μm to ± 5 microμm. apparatus. The electrolyzer according to any one of claims 1 to 5, wherein the thickness dimension of the thin plate-shaped foamed metal electrode is in the range of 0.05 mm to 0.5 mm. Claims 1 to 55, wherein the Fe-Ni content in the Fe-Ni permalloy is in the range of 45% to 55%, and the Ni content in the Fe-Ni permalloy is in the range of 45% to 55%. Item 6. The electrolysis device according to any one of. The electrolyzer according to any one of claims 1 to 7, wherein the porosity of the open cells formed on the thin plate-shaped foamed metal electrode is in the range of 45% to 55%. The thin plate density of the expanded metal ^electrode, electrolysis apparatus according to any one of claims 1 to 8 is in the range of ^{6.0g / cm 2 ~8.0g / cm 2} . The electrolyzer according to any one of claims 1 to 9, wherein the particle size of the permalloy fine powder is in the range of 1 μm to 100 μm.

Images