JP2020167041A - Electrode and manufacturing method thereof - Google Patents

Abstract

To provide an electrode which can fabricated at low cost without using a platinum-group element and which can exhibits a catalytic activity substantially at the same level as that of a platinum-group element-containing electrode.SOLUTION: An electrode 10 is composed of a thin plate-like porous metal electrode of a micro porous structure, in which permalloy fine powder melts and binds, and many fine continuous pores are evenly formed; the continuous pores are defined by a permalloy molten material which permalloy fine powder melts and binds into. The electrode is arranged by the steps of: uniformly mixing and dispersing a predetermined binder in permalloy fine powder prepared by finely pulverizing Fe-Ni permalloy and in parallel, uniformly mixing and dispersing a predetermined pore-forming material therein to make a permalloy fine powder mixture; molding the permalloy fine powder mixture having the binder and pore-forming material mixed in the permalloy fine powder in a thin plate-like form having a given area; and then, degreasing and sintering the resultant permalloy fine powder mixture mold shaped in the thin plate-like form.SELECTED DRAWING: Figure 1

Description

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

A fuel cell electrode in which platinum is supported on nitrogen-doped carbon obtained by calcining a porous metal complex (PCP / MOF) containing zinc, which is a low boiling metal, is disclosed (see Patent Document 1). Since this fuel cell electrode uses a porous metal complex (PCP / MOF) containing zinc, which is a low boiling metal, as a production raw material, it contains almost no metal derived from the raw material and is an NDC catalyst carrier having a large specific surface area. Can be obtained, and a highly active platinum catalyst can be obtained by supporting a small amount of platinum. Further, since the metal derived from the porous metal complex (PCP / MOF) which is a manufacturing raw material is not contained, the firing conditions can be freely set. That is, it is possible to control the nitrogen content and crystallinity in the obtained NDC by changing the organic compound linker of the porous metal complex (PCP / MOF) used as a raw material and adjusting the firing temperature.

Japanese Unexamined Patent Publication No. 2018-23929

Various platinum-supported carbons are widely used as electrode catalysts for polymer electrolyte fuel cells. 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 spread of polymer electrolyte fuel cells in the future, it is required to develop an inexpensive electrode having a non-platinum catalyst using a metal other than platinum, which is expensive.

An object of the present invention is an electrode that can be manufactured at low cost without using a platinum group element and can exhibit substantially the same catalytic activity (catalytic action) as an electrode containing a platinum group element, and an electrode of the electrode. The purpose is to provide a manufacturing method. Another object of the present invention is to be able to generate sufficient electricity in the fuel cell, to supply sufficient electrical energy to the load connected to the fuel cell, and to make electrolysis efficient in the hydrogen gas generator. It is an object of the present invention to provide an electrode which can be well performed and can generate a large amount of hydrogen gas, and an electrode manufacturing method for the electrode.

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

As a feature of the electrode of the present invention in the first premise, the electrode uniformly mixes and disperses a predetermined binder with permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy, and uniformly mixes a predetermined pore-forming material. A permalloy fine powder mixture that is dispersed and mixed with a binder and a pore-forming material in 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 sintered. As a result, 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, and has substantially the same catalytic activity (catalytic action) as an electrode containing a platinum group element. The open cells are defined by a permalloy melt in which permalloy fine powder is melt-bonded.

As an example of the electrode of the present invention, in the electrode, the Fe-Ni content in Fe-Ni permalloy and the Ni content in Fe-Ni permalloy are used so that the work function of the permalloy fine powder is close to the work function of the platinum group element. Has been decided.

As another example of the electrode of the present invention, open cells formed in 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. , 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 electrode 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, and one open cell and the other open cell communicate with each other. Then, the open cells adjacent to each other in the thickness direction and bent and extended 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 becomes , It 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 electrode 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 changes in the range of ± 0.1 μm to ± 5 microμm. ing.

As another example of the electrode 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 electrode 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 in the range of 45% to 55%. It is in.

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

As another example of the electrode 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 electrode of the present invention, the particle size of the permalloy fine powder is in the range of 1 μm to 100 μm.

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

The feature of the electrode manufacturing method of the present invention in the second premise is that the electrode manufacturing method is such that the work function of permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy is close to the work function of platinum group elements. -The content rate determination step for determining the Fe content and Ni content in Ni permalloy, and the Fe-Ni permalloy formed from Fe and Ni with the content rate determined by the content rate determination step are finely pulverized and permalloy. A predetermined binder and a predetermined pore-forming material are added to the permalloy fine powder preparation step for producing fine powder and the permalloy fine powder prepared by the permalloy fine powder preparation step, and the binder and the pore-forming material are uniformly mixed with the permalloy fine powder. Permalloy fine powder mixture preparation step to make a permalloy fine powder mixture by dispersing, and permalloy fine powder mixture preparation step to make a permalloy fine powder mixed mixture by molding the permalloy fine powder mixture prepared by the step to make a permalloy fine powder mixture into a thin plate. A large number of permalloy fine powders are melt-bonded by degreasing the permalloy fine powder mixed moldings prepared by the product preparation process and the permalloy fine powder mixed molding preparation process and sintering the permalloy fine powder mixed moldings at a predetermined temperature. A process for producing a thin plate-shaped foamed metal electrode having a microporous structure in which open cells are defined by a permalloy melt obtained by melt-bonding permalloy fine powder while fine continuous pores are evenly formed. To have.

As an example of the electrode manufacturing method of the present invention, the weight ratio determination step determines the Fe content in Fe-Ni permalloy in the range of 45% to 55%, and the Ni content in Fe-Ni permalloy is 45%. Determined in the range of ~ 55%.

As another example of the electrode manufacturing method of the present invention, the permalloy fine powder preparation step finely pulverizes Fe-Ni permalloy to a particle size of 1 μm to 100 μm.

As another example of the electrode manufacturing method of the present invention, a predetermined step of producing a permalloy fine powder mixed molded product has a thickness dimension of 0.05 mm to 0.5 mm by molding the permalloy fine powder mixed product by injection molding or extrusion molding. Make a permalloy fine powder mixed molded product with an area and a thin plate shape.

According to the electrode according to the present invention, the permalloy fine powder is obtained by uniformly mixing and dispersing a predetermined binder in a permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy and uniformly mixing and dispersing a predetermined pore-forming material. A permalloy fine powder mixture in which a binder and a pore-forming material are mixed is molded 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 sintered to form a permalloy fine powder. Is a thin plate-shaped foamed metal electrode with a microporous structure in which a large number of fine continuous pores are uniformly formed while being melt-bonded, and the electrode has substantially the same catalytic activity (catalytic action) as a fuel electrode or an air electrode containing a platinum group element. ), It is possible to exhibit excellent catalytic activity (catalytic action), and it can be suitably used as an electrode of a fuel cell or a hydrogen gas generator. The electrode is non-platinum that does not use expensive platinum group elements, and the cost of the electrode can be reduced.

The electrode in which the Fe content in Fe-Ni permalloy and the Ni content in Fe-Ni permalloy are determined so that the work function of the permalloy fine powder is close to the work function of the platinum group element is the permalloy fine powder. Since the Fe content and the Ni content in Fe-Ni permalloy are determined so that the work function of the body is close to the work function of the platinum group element, the electrode is abbreviated as an electrode carrying a platinum group element. Since it has the same work function and the electrode has substantially the same catalytic activity (catalytic action) as a fuel electrode or an air electrode containing a platinum group element, it has substantially the same catalytic activity (catalytic action) as an electrode carrying a platinum group element. It can be suitably used as an electrode of a fuel cell or a hydrogen gas generator. Since the electrode exhibits almost the same excellent catalytic activity (catalytic action) as the electrode carrying a platinum group element, it is possible to generate sufficient electricity in the fuel cell by using the electrode in the fuel cell. It is possible to supply sufficient electrical energy to the load connected to the fuel cell, and by using the electrodes in the hydrogen gas generator, it is possible to efficiently perform electrolysis and a large amount of hydrogen in a short time. Gas can be generated.

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. Since the electrode extending irregularly in the radial direction with the electrode has a plurality of continuous pores extending irregularly in the thickness direction and the radial direction, the specific surface area of the electrode is increased. Large, gas (oxygen and hydrogen) and liquid (water) can flow through these continuous pores, and the gas and liquid can be brought into wide contact with the contact surface of the continuous pores of the electrode, and the catalytic activity (catalytic action) of the electrode. Can be used effectively and to the maximum extent. Since the electrode has a large specific surface area and exhibits substantially the same catalytic activity (catalytic action) as an electrode carrying a platinum group element, it can be suitably used as an electrode for a fuel cell or a hydrogen gas generator. By using the electrodes in the fuel cell, it is possible to generate sufficient electricity in the fuel cell, supply sufficient electric energy to the load connected to the fuel cell, and use the electrodes as a hydrogen gas generator. By using it, electrolysis can be performed efficiently, and a large amount of hydrogen gas can be generated 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 bubble 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 the electrode 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 communicate with each other. Since the average diameter of these open cells changes irregularly in the thickness direction and the radial direction, the specific surface area of the electrode can be increased, and the continuous pores can be made into gas (oxygen and hydrogen) or liquid (water). ) Can flow through and a gas or liquid can be brought into contact with the contact surface of the continuous pores of the electrode in a wide range, and the catalytic activity (catalytic action) of the electrode can be effectively and maximized. Since the electrode has a large specific surface area and exhibits almost the same excellent catalytic activity (catalytic action) as the electrode carrying a platinum group element, it can be suitably used as an electrode of a fuel cell or a hydrogen gas generator. By using the electrodes in the fuel cell, it is possible to generate sufficient electricity in the fuel cell, supply sufficient electrical energy to the load connected to the fuel cell, and generate hydrogen gas in the electrodes. By using it in an apparatus, it is possible to efficiently perform electrolysis and generate a large amount of hydrogen gas in a short time.

The average diameter of the continuous pores formed on the thin plate-shaped foamed metal electrode is in the range of 1 μm to 100 μm, and the average diameter of the continuous pores of the electrode changing in the range of ± 0.1 μm to ± 5 microμm is described above. Since it is in the 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 electrode, the specific surface area of the electrode is large, and the continuous pores are gas (oxygen and hydrogen). Gas or liquid can be brought into contact with the contact surface of the continuous pores of the electrode in a wide range while flowing or liquid (water), and the catalytic activity (catalytic action) of the electrode can be effectively and maximized. Since the electrode has a large specific surface area and exhibits substantially the same catalytic activity (catalytic action) as an electrode carrying a platinum group element, it can be suitably used as an electrode for a fuel cell or a hydrogen gas generator. By using the electrodes in the fuel cell, it is possible to generate sufficient electricity in the fuel cell, supply sufficient electric energy to the load connected to the fuel cell, and use the electrodes as a hydrogen gas generator. By using it, electrolysis can be performed efficiently, and a large amount of hydrogen gas can be generated in a short time.

For electrodes in which the thickness dimension of the thin plate-shaped foamed metal electrode is in the range of 0.05 mm to 0.5 mm, the electrical resistance of the electrode can be reduced by setting the thickness dimension in the above range, and the current can be smoothly applied to the electrode. Can be flushed to. Since the electrode has almost the same excellent catalytic activity (catalytic action) as the electrode carrying a platinum group element and the current flows smoothly through it, it is sufficient in the fuel cell to use the electrode in the fuel cell. Electricity can be generated, sufficient electric energy can be supplied to the load connected to the fuel cell, and by using the electrodes in the hydrogen gas generator, the electrolysis is efficient in the hydrogen gas generator. It can be done well and a large amount of hydrogen gas can be generated in a short time.

Electrodes 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% have a platinum work function of permalloy fine powder. Since the Fe content and the Ni content in Fe-Ni permalloy are determined within the above range so as to approximate the work function of the group element, the electrode has substantially the same work as the electrode carrying the platinum group element. It has a function and can exhibit excellent catalytic activity (catalytic action) that is almost the same as an electrode carrying a platinum group element, and it is possible to fully and surely utilize the catalytic function and has excellent catalytic activity (excellent catalytic activity (catalytic action). It can be suitably used as a non-platinum anode or a cathode having a catalytic action).

The porosity of the open cells formed on the thin plate-shaped foamed metal electrode is in the range of 45% to 55%. By setting the porosity of the thin plate-shaped foamed metal electrode (electrode) to the above range, the thin plate-shaped foamed metal The electrode is 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 uniformly and uniformly formed), and the specific surface area of the electrode can be increased. While gas (oxygen and hydrogen) and liquid (water) pass through these continuous pores, gas and liquid can be brought into contact with the contact surface of the electrode over a wide range, and the catalytic activity is almost the same as that of an electrode carrying a platinum group metal. (Catalytic action) can be reliably exerted. The electrode can be suitably used as a non-platinum anode or cathode having excellent catalytic activity (catalytic action) and can fully and reliably utilize its catalytic function.

Electrode by the density of the thin foamed metal electrode on the range, continuous electrode is many fine density of the sheet-like porous metal electrode is in the range of 6.0g ^/ cm ² ~8.0g / cm 2 It is formed into a porous structure with pores (a microporous structure in which fine continuous pores with an average diameter of 1 μm to 100 μm are formed evenly and uniformly), and the specific surface area of the electrode can be increased, and these continuous pores are made into gas (oxygen). And hydrogen) and liquid (water) can pass through, and gas and liquid can be brought into contact with the contact surface of the continuous pores of the electrode over a wide range, and the catalytic activity (catalytic action) is almost the same as that of the electrode carrying the white metal element. ) Can be demonstrated reliably. The electrode can be suitably used as a non-platinum anode or cathode having excellent catalytic activity (catalytic action) and can utilize its catalytic function to the maximum extent and surely.

Electrodes having a particle size of Permalloy fine powder in the range of 1 μm to 100 μm are porous (average diameter is 1 μm to 100 μm) having a large number of fine continuous pores by setting the particle size of Permalloy fine powder to the above range. It is formed into a microporous structure in which fine continuous pores are evenly and uniformly formed), and the specific surface area of the electrode can be increased, while gas (oxygen and hydrogen) and liquid (water) pass through these continuous pores. It is possible to bring a gas or liquid into contact with the contact surface of the continuous pores of the electrode over a wide range, and it is possible to reliably exhibit the catalytic activity (catalytic action) substantially similar to that of the electrode carrying the white metal element. The electrode can be suitably used as a non-platinum anode or cathode having excellent catalytic activity (catalytic action), which can make full use of its catalytic function.

According to the electrode manufacturing method according to the present invention, the content of Fe in Fe-Ni permalloy and the work function of Ni so that the work function of permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy is close to the work function of platinum group elements. A content rate determination step for determining the content rate, a permalloy fine powder preparation step for producing permalloy fine powder by finely pulverizing Fe-Ni permalloy formed from Fe and Ni having a content rate determined by the content rate determination step. A predetermined binder and a predetermined pore-forming material are added to the permalloy fine powder prepared by the permalloy fine powder preparation step, and the binder and the pore-forming material are uniformly mixed and dispersed in the permalloy fine powder to prepare a permalloy fine powder mixture. Permalloy fine powder mixed molding making step and permalloy fine powder mixed molding making step to make permalloy fine powder mixed molded product by molding the permalloy fine powder mixed mixed made by the fine powder mixed making step into a thin plate shape, and permalloy fine powder mixed molding The permalloy fine powder mixed molded product prepared in the product preparation process is degreased and the permalloy fine powder mixed molded product is sintered at a predetermined temperature, and a large number of fine continuous pores are evenly formed while the permalloy fine powder is melt-bonded. At the same time, the electrode is manufactured by each step of making a thin plate-shaped foamed metal electrode having a microporous structure in which open cells are defined and surrounded by a permalloy melt in which permalloy fine powder is melt-bonded. , The electrode can be made at a low cost, has substantially the same work function as the electrode carrying the platinum group element, and exhibits almost the same excellent catalytic activity (catalytic action) as the electrode carrying the platinum group element. It is possible to make a non-platinum electrode (anode or a cathode) capable of making a non-platinum electrode capable of fully and surely utilizing the catalytic function. In the electrode manufacturing method, since the electrode produced by the electrode exhibits substantially the same catalytic activity (catalytic action) as the electrode carrying platinum, it is possible to generate sufficient electricity in the fuel cell, and the fuel cell can be used. It is possible to make electrodes that can supply sufficient electrical energy to the connected load, and it is possible to efficiently perform electrolysis in a hydrogen gas generator and generate a large amount of hydrogen gas in a short time. It is possible to make an electrode that can be made to.

An electrode manufacturing method in which the content rate determination step determines the Fe content in Fe-Ni permalloy in the range of 45% to 55% and the Ni content in Fe-Ni permalloy in the range of 45% to 55%. Since the Fe content and Ni content in Fe-Ni permalloy are determined in the above range in the content rate determination step so that the work function of the permalloy fine powder is close to the work function of the platinum group element, the platinum group It is possible to make a non-platinum electrode (anode or cathode) capable of exhibiting almost the same excellent catalytic activity (catalytic action) as an electrode carrying an element, and it is possible to fully and surely utilize the catalytic function. Possible non-platinum electrodes can be made.

There are many electrode manufacturing methods in which the permalloy fine powder preparation process finely grinds Fe-Ni permalloy to a particle size of 1 μm to 100 μm by finely grinding Fe-Ni permalloy and setting the particle size of the permalloy fine powder within the above range. It is possible to make an electrode formed into a porous material having 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 to make an electrode having a large specific surface area. At the same time, it is possible to make an electrode capable of bringing the gas or liquid into wide contact with the contact surface in the continuous pores while allowing the gas (oxygen and hydrogen) or the liquid (water) to pass through the continuous pores.

Electrode in which the Permalloy fine powder mixed molded product preparation process forms a Permalloy fine powder mixed molded product by injection molding or extrusion molding to produce a permalloy fine powder mixed molded product having a predetermined area and a thin plate shape having a thickness dimension of 0.05 mm to 0.5 mm. The manufacturing method is a microporous structure and thin plate-shaped electrode having a large number of fine continuous pores by degreasing and sintering a fine powder mixed molded product having a thickness dimension of 0.05 mm to 0.5 mm obtained by molding the fine powder mixed mixture. Non-platinum, which has a microporous structure and a thin plate-like electrode at a low cost, has excellent catalytic activity (catalytic action), and can sufficiently and reliably utilize the catalytic function. Electrodes (anolyte or catalyst) can be made. In the electrode manufacturing method, since an electrode having a thickness in the range of 0.05 mm to 0.5 mm can be produced, an electrode (anode or an anode or an electrode having high proton conductivity) that has low electrical resistance and can smoothly flow an electric current. Cathode) can be made.

The perspective view of the electrode shown as an example. The partially enlarged view which shows as an example of an electrode. An exploded perspective view showing an example of a cell using electrodes. Side view of the cell using electrodes. The figure explaining the power generation of the polymer electrolyte fuel cell using an electrode. The figure which shows the result of the electromotive force test of an electrode. The figure which shows the result of the IV characteristic test of an electrode. The figure explaining the electrolysis of the hydrogen gas generator using an electrode. The figure explaining the manufacturing method of an electrode.

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

The electrode 10 is used as an anode or a cathode, and has a fuel electrode 18 (catalyst electrode) and an air electrode 19 (catalyst electrode) (see FIG. 5) of the polymer electrolyte fuel cell 17, and an anode 31 (electrode) of the hydrogen gas generator 30. It is used as a catalyst) or a cathode 32 (electrode catalyst) (see FIG. 8). The electrode 10 has a front surface 11 and a rear surface 12, has a predetermined area and a predetermined thickness dimension L1, and its planar shape is formed into a quadrangle. The electrode 10 is a porous (microporous structure) thin plate-shaped foamed metal electrode in which a large number of fine continuous pores 13 (continuous ventilation holes) are uniformly and uniformly formed. Gas (oxygen and hydrogen) and liquid (water) pass through the continuous pores 13. The planar shape of the electrode 10 is not particularly limited, and it can be formed into any other planar shape such as a circle, an ellipse, or a polygon according to the intended use, in addition to the quadrangle.

The electrode 10 is formed of Fe—Ni permalloy 41 that has been finely pulverized (pulverized) into powder. A predetermined binder 43 (powdered resin-based binder) is mixed with the permalloy fine powder 42 (Fe-Ni permalloy 41 processed into fine powder) of Fe-Ni permalloy 41, and the permalloy fine powder 42 and the binder 43 are made uniform. To prepare a fine powder mixture 45 mixed and dispersed in, and further, a predetermined pore-forming material 44 (foaming agent) is mixed with the fine powder mixture 45 to prepare a fine powder mixture 45 in which the pore-forming material 44 is uniformly mixed and dispersed. .. The prepared fine powder mixture 45 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 fine powder mixed molded product 46, and the prepared fine powder mixed molded product 46 is used. The electrode 10 is made by degreasing and sintering (baking) at a predetermined temperature (see FIG. 9). The open cell 13 is defined and surrounded by a permalloy melt in which the permalloy fine powder 42 is melt-bonded.

At the electrode 10, the Fe (iron) in the Fe—Ni permalloy 41 (relative to the total weight (100%) of the Fe—Ni permalloy 41) so that the work function of the permalloy fine powder 42 approximates the work function of the platinum group element. The content rate (weight ratio) and the Ni (nickel) content rate (weight ratio) have been determined. Specifically, the Fe content (weight ratio) in Fe-Ni permalloy 41 is in the range of 45% to 55%, preferably in the range of 49% to 51%, and the content of Ni in Fe-Ni permalloy 41. 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 in the Fe-Ni permalloy 41 and the Ni content in the Fe-Ni permalloy 41 are out of the above range, the working function of the permalloy fine powder 42 cannot be approximated to the working function of the platinum group element. The electrode 10 produced by degreasing and sintering (baking) the fine powder mixed molded product 46 obtained by molding the fine powder mixed mixture 45 exhibits substantially the same catalytic activity (catalytic action) as an electrode carrying a platinum group element. I can't.

Since the Fe content and Ni content in Fe-Ni Permalloy 41 are in the above range so that the work function of the permalloy fine powder 42 is close to the work function of the platinum group element, the electrode 10 is a platinum group element ( It has substantially the same work function as the electrode carrying (including platinum), and the electrode 10 exhibits almost the same excellent catalytic activity (catalytic action) as the electrode carrying (including) a platinum group element (platinum). Can be done.

A large number of fine continuous pores 13 (continuous ventilation holes) having different diameters are formed in the electrode 10. Since the electrode 10 is formed with a large number of fine continuous pores 13, its specific surface area is large. The continuous pores 13 formed in the thin plate-shaped foamed metal electrode have a plurality of passage ports 14 that open in the front surface 11 of the electrode 10 and a plurality of passage ports 14 that open in the rear surface 12 of the electrode 10. The electrode 10 penetrates from the front surface 11 to the rear surface 12 of the electrode 10 in the thickness direction thereof, and also penetrates in the radial direction from the center of the electrode 10 toward the outer peripheral edge 15.

The continuous pores 13 extend between the front surface 11 and the rear surface 12 of the electrode 10 while being irregularly bent in the thickness direction of the electrode 10, and the diameter of the electrode 10 is extended from the outer peripheral edge 15 of the electrode 10 toward the center. It extends in an irregular direction. The continuous pores 13 (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 13 and the other pore 13 communicate with each other. The continuous pores 13 (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 13 and the other pore 13 communicate with each other.

The average diameter (opening area) of these continuous pores 13 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 13 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 14 opened in the front surface 11 of the electrode 10 and the air flow port 14 opened in the rear surface 12 is not uniform, and the average diameters are all different. The average diameter (opening area) of the continuous pores 13 and the average diameter (opening area) of the passage ports 14 of the front and rear surfaces 11 and 12 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 13).

The electrode 10 is formed with a plurality of continuous pores 13 (continuous ventilation holes) extending while irregularly bending in the thickness direction and the radial direction, and the average diameter of the pores 13 is in the range of 1 to 100 μm (preferably 45 μm to 55 μm). Since the range of change in the average diameter of the continuous pores 13 is in the range of ± 0.1 μm to ± 5 μm, a large number of continuous pores 13 are formed per unit volume of the electrode 10, and the specific surface area of the electrode 10 is increased. Can be enlarged, and the gas (gas) or liquid can be brought into contact with the contact surface of the pores 25 of the electrode 10 over a wide range while the gas (gas) or liquid is flowing through the pores 13, and the catalyst of the electrode 10 can be contacted. The activity (catalytic action) can be effectively and maximized.

The electrode 10 (thin plate-shaped foamed metal electrode having a microporous structure) has a thickness dimension L1 in the range of 0.05 mm to 0.5 mm. If the thickness dimension L1 of the electrode 10 is less than 0.05 mm, its strength is lowered, and the electrode 10 may be easily damaged or damaged when an impact is applied, and its shape may not be maintained. When the thickness dimension L1 of the electrode 10 exceeds 0.5 mm, the electrical resistance of the electrode 10 increases, the current does not flow smoothly through the electrode 10 (proton conductivity is low), and the electrode 10 is a solid polymer fuel cell 17 The fuel cell 17 cannot generate sufficient electricity when used in the fuel cell 17, and cannot supply sufficient electric energy to the load 29 connected to the fuel cell 17. Further, when the electrode 10 is used in the hydrogen gas generator 30, electrolysis cannot be efficiently performed, and the hydrogen gas generator 30 cannot generate a large amount of hydrogen gas in a short time.

Since the thickness dimension L1 of the electrode 10 is in the range of 0.05 mm to 0.5 mm, the electrode 10 has high strength and can maintain its shape, and when an impact is applied to the electrode 10. It is possible to prevent the electrode 10 from being damaged or damaged. Further, the electrical resistance of the electrode 10 can be reduced, a current flows smoothly through the electrode 10 (high proton conductivity), and when the electrode 10 is used in the polymer electrolyte fuel cell 17, the fuel cell 17 Sufficient electricity can be generated, and sufficient electric energy can be supplied to the load 29 connected to the fuel cell 17. Further, when the electrode 10 is used in the hydrogen gas generator 30, electrolysis can be efficiently performed, and the hydrogen gas generator 30 can generate a large amount of hydrogen gas in a short time.

The electrode 10 (thin plate-shaped foamed metal electrode having a microporous structure) has a porosity in the range of 45% to 55%. If the pore ratio of the electrode 10 is less than 45%, a large number of fine continuous pores 13 (continuous ventilation holes) are not formed in the electrode 10, and the specific surface area of the electrode 10 cannot be increased. When the porosity of the electrode 10 exceeds 55%, the average diameter (opening area) of the continuous pores 13 (continuous ventilation holes) and the average diameter (opening area) of the passage ports 14 of the front and rear surfaces 11 and 12 become larger than necessary. As a result, the strength of the electrode 10 decreases, and when an impact is applied, the electrode 10 may be easily damaged or damaged, and its shape may not be maintained, and the catalytic action of the electrode 10 decreases, resulting in a catalyst. Cannot exert activity.

Since the porosity of the electrode 10 is in the above range, the electrode 10 has a large number of fine continuous pores 13 having different average diameters (opening areas) (the average diameter is in the range of 1 to 100 μm, preferably in the range of 45 μm to 55 μm). Continuous pores 13) and a large number of fine front and rear surfaces 11 and 12 having different average diameters (opening areas) 14 (average diameter in the range of 1 to 100 μm, preferably in the range of 45 μm to 55 μm) It is formed into a porous material (microporous structure) having 14), and the specific surface area of the electrode 10 can be increased, and the gas or liquid comes into contact with the pores 13 of the electrode 10 while the gas or liquid flows through the pores 13. Can be widely contacted with the surface. Further, the catalytic action of the electrode 10 is improved, and excellent catalytic activity can be exhibited.

Electrode 10 (thin plate porous metal electrodes 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 ~7.5g / cm} 2 Is in the range of. If the density of the electrode 10 is less than 6.0 g / cm ² (6.5 g / cm ² ), the strength of the electrode 10 decreases, and the electrode 10 is easily damaged or damaged when an impact is applied, and the shape thereof is changed. In some cases, it cannot be maintained, and the catalytic action of the electrode 10 is reduced, so that the catalytic activity cannot be exhibited. When the density of the electrode 10 exceeds 8.0 g / cm ² (7.5 g / cm ² ), a large number of fine continuous pores 13 and a large number of fine passage ports 14 are not formed in the electrode 10, and the electrode 10 is formed. The specific surface area cannot be increased, and the catalytic action of the electrode 10 is reduced, so that the catalytic activity cannot be exhibited.

Since the density of the electrode 10 is in the above range, the electrode 10 has a large number of fine continuous pores 13 having different average diameters (opening areas) (the average diameter is in the range of 1 to 100 μm, preferably in the range of 45 μm to 55 μm). Passage ports 14 (with an average diameter in the range of 1 to 100 μm, preferably in the range of 45 μm to 55 μm) of a large number of fine front and rear surfaces 11 and 12 having continuous pores 13) and different average diameters (opening areas) ) Is formed into a porous material (microporous structure), the specific surface area of the electrode 10 can be increased, and the contact surface of the electrode 10 in the pores 13 while the gas or liquid flows through the pores 13. Can be widely contacted with, and the catalytic action of the electrode 10 can be effectively and maximized. Further, the catalytic action of the electrode 10 is improved, and the electrode 10 can exhibit excellent catalytic activity.

The particle size of the permalloy fine powder 42 (Fe-Ni permalloy 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 42 is less than 1 μm, the continuous pores 13 (continuous ventilation holes) are blocked by the permalloy fine powder 42, and a large number of fine continuous pores 13 cannot be formed in the electrode 10, so that the electrode 10 cannot be formed. The specific surface area of the electrode 10 cannot be increased, and the catalytic action of the electrode 10 is reduced, so that the catalytic activity cannot be exhibited. When the particle size of the permalloy fine powder 42 exceeds 100 μm, the average diameter (opening area) of the continuous pores 13 and the average diameter (opening area) of the passage ports 15 of the front and rear surfaces 11 and 12 become larger than necessary, and the electrode 10 It is not possible to form a large number of fine continuous pores 13 in the electrode 10, the specific surface area of the electrode 10 cannot be increased, and the catalytic action of the electrode 10 is lowered, so that the catalytic activity cannot be exhibited.

Since the particle size of the permalloy fine powder 42 is in the above range, the electrode 10 has a large number of fine continuous pores 13 (with an average diameter of 1 to 100 μm, preferably 45 μm) having different average diameters (opening areas). Continuous pores 13) in the range of ~ 55 μm and through ports 14 (average diameter in the range of 1 to 100 μm, preferably in the range of 45 μm to 55 μm) of a large number of fine front and rear surfaces 11 and 12 having different average diameters (opening areas). It is formed into a porous material (microporous structure) having a passage port 14), and the specific surface area of the electrode 10 can be increased, and the gas or liquid is passed through the pores 13 while the gas or liquid is passed through those of the electrode 10. The contact surface in the pores 13 can be widely contacted, and the catalytic activity (catalytic action) of the electrode 10 can be effectively and maximized. Further, the catalytic action of the electrode 10 is improved, and the electrode 10 can exhibit excellent catalytic activity.

FIG. 3 is an exploded perspective view showing an example of the cell 16 using the electrode 10, and FIG. 4 is a side view of the cell 16 using the electrode 10. FIG. 5 is a diagram illustrating power generation of the polymer electrolyte fuel cell 17 using the electrode 10, and FIG. 6 is a diagram showing the results of an electromotive voltage test of the electrode 10. FIG. 7 is a diagram showing the results of the IV characteristic test of the electrode 10.

As an example of the cell 16 using the electrode 10, as shown in FIG. 3, a fuel electrode 18 (anode) using the electrode 10, an air electrode 19 (cathode) using the electrode 10, a fuel electrode 18 and air The solid polymer electrolyte membrane 20 (electrode junction membrane) (fluorine-based ion exchange membrane) interposed at the pole 19, the separator 21 (bipolar plate) located outside in the thickness direction of the fuel pole 18, and the thickness direction of the air pole 19 It is formed from a separator 22 (bipolar plate) located on the outside. Supply channels for reaction gases (hydrogen, oxygen, etc.) are engraved (engraved) in the separators 21 and 22.

In the cell 16, as shown in FIG. 4, the fuel electrode 18, the air electrode 19, and the solid polymer electrolyte membrane 20 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly 23 (MEA). The membrane / electrode assembly 23 is sandwiched between the separators 21 and 22. In the membrane / electrode assembly 23, the surface of the fuel electrode 18 is closely adhered to one surface of the solid polymer electrolyte membrane 20 by hot pressing, and the surface of the air electrode 19 is attached to the other surface of the solid polymer electrolyte membrane 20. It is in close contact without any gaps. In the polymer electrolyte fuel cell 17, a plurality of cells 16 (single cells) are overlapped in one direction and connected in series to form a cell stack (fuel cell stack). The solid polymer electrolyte membrane 20 has proton conductivity and no electron conductivity.

A gas diffusion layer 24 is formed between the fuel electrode 18 and the separator 21, and a gas diffusion layer 25 is formed between the air electrode 19 and the separator 22. Gas seals 26 are installed between the fuel electrode 18 and the separator 21 at the upper and lower parts of the gas diffusion layer 24. Gas seals 27 are installed between the air electrode 19 and the separator 22 at the upper and lower parts of the gas diffusion layer 25.

In the polymer electrolyte fuel cell 17, as shown in FIG. 5, hydrogen (fuel) is supplied to the fuel electrode 18 (electrode 10), and air (oxygen) is supplied to the air electrode 19 (electrode 10). At the fuel electrode 18 (electrode 10), hydrogen is decomposed into protons (hydrogen ions, H ⁺ ) and electrons by the reaction (catalysis) of H ₂ → 2H ⁺ + 2e ⁻ . After that, protons move through the solid polymer electrolyte membrane 20 to the air electrode 19 (electrode 10), and electrons move through the lead wire 28 to the air electrode 19. Protons generated at the fuel electrode 18 pass through the solid polymer electrolyte membrane 20. At the air electrode 19, the protons transferred from the solid polymer electrolyte membrane 20 and the electrons transferred through the lead wire 28 react with oxygen in the air, and water is generated by the reaction of 4H ⁺ + O ₂ + 4e → 2H ₂ O.

The fuel electrode 18 (electrode 10) and the air electrode 19 (electrode 10) are Fe in Fe-Ni permalloy so that the work function of the permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy is close to the work function of the platinum group element. Since the content (weight ratio) of Ni and the content (weight ratio) of Ni are determined, the electrode 10 (fuel electrode 18 (anode) and air electrode 19 (catalyst)) carries a platinum group element (platinum). It has almost the same work function as the electrode (including), and shows almost the same excellent catalytic activity (catalytic action) as the electrode carrying a platinum group element (platinum), and hydrogen is efficiently decomposed into protons and electrons. To.

In the electromotive voltage test, the voltage (V) between the fuel electrode 18 (electrode 10) and the air electrode 19 (electrode 10) (between the electrodes 10) was measured for 15 minutes after the hydrogen gas was injected. In the figure showing the result of the electromotive force test of FIG. 6, the horizontal axis represents the measurement time (min), and the vertical axis represents the voltage (V) between the electrodes. In a polymer electrolyte fuel cell using (supported) a fuel electrode using a platinum group element or an air electrode (platinum electrode), the fuel electrode and the air electrode can be seen from FIG. 6 showing the results of the electromotive voltage test. The voltage between and (between electrodes) was around 1.079 (V). On the other hand, in the polymer electrolyte fuel cell 10 using the fuel electrode 18 (non-platinum electrode 10) and the air electrode 19 (non-platinum electrode 10), between the fuel electrode 18 and the air electrode 19 (between the electrodes 10). The voltage (electromotive force) of) was 0.98 (V) to 1.02 (V).

In the IV characteristic test, a load 29 was connected between the fuel electrode 18 (electrode 10) and the air electrode 19 (electrode 10) (between the electrodes 10), and the relationship between the voltage and the current was measured. In the figure showing the result of the IV characteristic test of FIG. 7, the horizontal axis represents the current (A) and the vertical axis represents the voltage (V). In the polymer electrolyte fuel cell 10 using the fuel electrode 18 (non-platinum electrode 10) and the air electrode 19 (non-platinum electrode 10), platinum can be seen from FIG. 7 showing the results of the IV characteristic test. Results were obtained that were not much different from the voltage drop rate of polymer electrolyte fuel cells that used (supported) fuel electrodes and air electrodes (platinum electrodes) that used group elements. As shown in the result of the electromotive voltage test of FIG. 6 and the result of the IV characteristic test of FIG. 6, the non-platinum fuel electrode 18 (non-platinum electrode 10) and the air electrode 19 (non-platinum electrode 10) that do not use platinum group elements are used. The non-platinum electrode 10) has an excellent catalytic action that promotes the reaction of releasing electrons to become hydrogen ions, and has an oxygen reduction function (catalyst) that is almost the same as the fuel electrode and air electrode (platinum electrode) using platinum. It was confirmed that it has an action).

The electrode 10 is formed of Fe-Ni permalloy 41, and the predetermined pore-forming material 44 is uniformly mixed and dispersed in the permalloy fine powder 42 obtained by finely pulverizing the Fe-Ni permalloy 41 while the predetermined binder 43 is uniformly mixed and dispersed. A permalloy fine powder mixture 45, which is mixed and dispersed and mixed with a binder 43 and a pore forming material 44 in a permalloy fine powder 42, is formed into a thin plate having a predetermined area, and then formed into a thin plate having a predetermined area. A thin plate-shaped foamed metal electrode 10 having a microporous structure in which a large number of fine continuous pores 13 are evenly and uniformly formed by degreasing and sintering 46, and a permalloy fine powder 42 in which these continuous pores 13 are melt-bonded. It is defined and surrounded by the permalloy melt, and the Fe-Ni permalloy 41 contains Fe (weight ratio) and Ni so that the work function of the permalloy fine powder 42 is close to the work function of the platinum group element. Since the ratio (weight ratio) is determined, by utilizing the catalytic activity of Fe-Ni permalloy 41, it is possible to exhibit excellent catalytic activity (catalytic action) substantially similar to that of an electrode carrying a platinum group element. It can be suitably used as a fuel pole 18 (anode) or an air pole 19 (cathode) having excellent catalytic activity (catalytic action) and capable of sufficiently and surely utilizing its catalytic function. ..

Since the electrode 10 exhibits almost the same excellent catalytic activity (catalytic action) as the electrode carrying the white metal element, the electrode 10 can be used in the polymer electrolyte fuel cell 17 in the fuel cell 17. Sufficient electricity can be generated, and sufficient electric energy can be supplied to the load 29 connected to the fuel cell 17. Since the electrode 10 is made of permalloy fine powder 42 obtained by finely pulverizing Fe-Ni permalloy 41, an expensive platinum group element (platinum (Pt)) is not used, and the material cost of the electrode 10 is reduced. It can be reduced, and the electrode 10 (fuel electrode 18 (anode) and air electrode 19 (cathode)) can be made at low cost.

FIG. 8 is a diagram illustrating electrolysis of the hydrogen gas generator 30 using the electrode 10. As an example of the hydrogen gas generator 30 using the electrode 10, as shown in FIG. 8, the anode 31 (anode) using the electrode 10, the cathode 32 (anode) using the electrode 10, the anode 31 and the cathode A solid polymer electrolyte film 33 (electrode junction film) (fluorine-based ion exchange film) interposed between 32, an anode feeding member 34 and a cathode feeding member 35, and an anode water storage tank 36 and a cathode water storage tank 37. , The anode main electrode 38 and the cathode main electrode 39.

In the hydrogen gas generator 30, the anode 31 (anode), the cathode 32 (cathode), and the solid polymer electrolyte membrane 33 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly 40 (MEA). , The membrane / electrode assembly 40 is sandwiched between the anode feeding member 34 and the cathode feeding member 35. The solid polymer electrolyte membrane 33 has proton conductivity and no electron conductivity. In the membrane / electrode assembly 40, the surface of the cathode 32 (cathode) is in close contact with one surface of the solid polymer electrolyte membrane 33 without a gap by hot pressing, and the anode 31 (anode) is attached to one surface of the solid polymer electrolyte membrane 20. ) Surfaces are in close contact with each other.

The anode feeding member 34 is located outside the anode 31 (anode) and is in close contact with the anode 31 to supply a positive current to the anode 31. The water storage tank 36 for the anode is located outside the anode feeding member 34 and is in close contact with the anode feeding member 34. The anode main electrode 38 is located outside the anode water storage tank 36 and supplies a positive current to the anode feeding member 34. The cathode feeding member 35 is located outside the cathode 32 (cathode) and is in close contact with the cathode 32 to supply a negative current to the cathode 32. The cathode water storage tank 37 is located outside the cathode feeding member 35 and is in close contact with the cathode feeding member 35. The cathode main electrode 39 is located outside the cathode water tank 37 and supplies a negative current to the cathode feeding member 35.

In the hydrogen gas generator 30, as shown by an arrow in FIG. 8, water (H ₂ O) is supplied to the anode water storage tank 36 and the cathode water storage tank 37, and a positive current is supplied to the anode main electrode 38 from the power supply. At the same time, a negative current is supplied to the cathode main electrode 39 from the power source. The positive current fed to the anode main electrode 38 is fed from the anode feeding member 34 to the anode 31 (anode), and the negative current fed to the cathode main electrode 39 is fed from the cathode feeding member 35 to the cathode 32 (cathode). Will be done.

At the anode 31 (anode) (electrode 10), oxygen is generated by the anode reaction (cathode) of 2H ₂ O → 4H ⁺ + 4e ⁻ + O ₂ , and at the cathode 32 (cathode) (electrode 10), 4H ⁺ + 4e ⁻ → oxygen is produced by the cathodic reaction of 2H ₂ (catalytic). Protons (hydrogen ions: H ⁺ ) move through the solid polymer electrolyte membrane 33 to the cathode 32. Protons generated at the anode 31 pass through the solid polymer electrolyte membrane 33.

The electrode 10 (anode 31 and cathode 32) has an Fe content in the Fe-Ni permalloy 41 so that the work function of the permalloy fine powder 42 obtained by finely pulverizing the Fe-Ni permalloy 41 is close to the work function of the platinum group element. Since the (weight ratio) and the Ni content (weight ratio) are determined, the electrodes 10 (anode 31 and cathode 32) have substantially the same work function as the electrodes carrying the platinum group element (platinum). It is possible to exhibit almost the same excellent catalytic activity (catalytic action) as an electrode carrying a platinum group element, and it is possible to fully and surely utilize the catalytic function, and the excellent catalytic activity (catalytic action). It can be suitably used as an electrode 31 (electrode) and a cathode 32 (cathode) having the above.

Since the electrode 10 (anode 31 and cathode 32) exhibits substantially the same excellent catalytic activity (catalytic action) as the electrode carrying a platinum group element, hydrogen gas is generated from the electrode 10 (anode 31 and cathode 32). By using it in the apparatus 30, electrolysis can be efficiently performed in the hydrogen gas generator 30, and a large amount of hydrogen gas can be generated in a short time. Since the electrode 10 (anode 31 and cathode 32) is made of permalloy fine powder 42 obtained by finely pulverizing Fe-Ni permalloy 41, an expensive platinum group element (platinum (Pt)) is not used. The material cost of the electrode 10 can be reduced, and the electrode 10 (anode 31 and cathode 32) can be manufactured at low cost.

FIG. 9 is a diagram illustrating a method for manufacturing the electrode 10. As shown in FIG. 9, the electrodes 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) 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. It is manufactured by an electrode manufacturing method having a mixed molded product manufacturing step S4 and a thin plate foam metal electrode manufacturing step S5. In the electrode manufacturing method, the electrode 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) is manufactured using Fe-Ni permalloy 42 as a raw material.

In the content rate determination step S1, the Fe-Ni permalloy 41 contains Fe and Ni so that the work function of the permalloy fine powder 42 obtained by finely pulverizing Fe-Ni permalloy 41 is close to the work function of the platinum group element. Determine the rate. The Fe content in Fe-Ni permalloy 41 is determined in the range of 45% to 55%, preferably 49% to 51%, and the Ni content in Fe-Ni permalloy 41 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 41 formed from Fe and Ni having a content determined by the content rate determination step is finely pulverized to produce permalloy fine powder 42. Fe-Ni permalloy 41 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 42.

The electrode manufacturing method is a porosity having a large number of fine continuous pores 13 (continuous ventilation holes) by finely pulverizing Fe-Ni Permalloy 41 to a particle size of 1 μm to 100 μm, preferably 30 μm to 60 μm. It is possible to form a thin plate-shaped foamed metal electrode 10 having a microporous structure having a large specific surface area, and the gas or liquid is passed through the continuous pores 13 of the electrode 10 while the gas or liquid is flowing through the continuous pores 13. Electrodes 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) that can be brought into contact with the contact surface in a wide range can be formed.

In the permalloy fine powder mixture preparation step S3, a predetermined binder 43 and a predetermined pore forming material 44 are added to the permalloy fine powder 42 prepared in the permalloy fine powder preparation step S2, and the binder 43 and the pore forming material 44 are added to the permalloy fine powder 42. Is uniformly mixed and dispersed to prepare a permalloy fine powder mixture 45. Since no expensive platinum group metal (platinum (Pt)) is used in the electrode manufacturing method, the electrode 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) can be produced at low cost.

In the permalloy fine powder mixture preparation step S3, the permalloy fine powder 42 of Fe-Ni permalloy 41 and the binder 43 (powder-based resin binder) are put into a mixer or agitator, and the Fe-Ni permalloy 41 is added by the mixer or agitator. Permalloy fine powder 42 and the binder 43 are stirred and mixed to prepare a fine powder mixture 45 (foam metal molding material) in which the permalloy fine powder 42 and the binder 43 are uniformly mixed and dispersed. Next, a predetermined amount of the pore-forming material 44 (powder foaming agent) is mixed (added) into the fine powder mixture 45. A predetermined amount of the pore-forming material 44 is put into a mixer or a stirrer, and the fine powder mixture 45 (foam metal molding material) is prepared by uniformly mixing and dispersing the pore-forming material 44 in the fine powder mixture 45 by the mixer or the stirrer. .. The average diameter and porosity of the continuous pores 13 formed in the electrode 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) are determined by the amount (addition amount) of the pore forming material 44 (powder foaming agent) mixed in. It is decided.

In the Permalloy fine powder mixed molding preparation step S4, the fine powder mixture 45 (foam metal molding material) prepared by 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 fine powder mixture 45 is injection-molded by an injection molding machine, or the fine powder mixture 45 is extruded by an extrusion molding machine, and the fine powder mixture 45 is formed into a thin plate having a predetermined area (thickness dimension L1 is 0.05 mm). A fine powder mixed molded product 46 (foamed metal molded product) molded into a range of ~ 0.5 mm is produced.

In the thin plate-shaped foamed metal electrode producing step S5, the permalloy fine powder mixed molded product 46 (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 46 is put into a firing furnace (combustion furnace, electric furnace, etc.), and the permalloy fine powder mixed molded product 46 is sintered (baked) at a predetermined temperature at a predetermined temperature for a predetermined time, and a large number of fine continuous pores 13 are obtained. (Continuous vent holes) are evenly and uniformly formed, and the thin plate-shaped foamed metal electrode 10 (thickness dimension L1) having a microporous structure defined and surrounded by the permalloy melt of the permalloy fine powder 42 in which the open cells 13 are melt-bonded. An electrode 10 of 0.05 mm to 0.5 mm (fuel electrode 18, air electrode 19, anode 31 and cathode 32) is made.

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 52 (foamed metal molded product) molded into a thin plate shape having a predetermined area is sintered, the pore-forming material is inside the permalloy fine powder mixed molded product 46. After the 44 (powder foaming agent) foams, the pore forming material 44 disappears from the inside of the permalloy fine powder mixed molded product 46, and a large number of fine continuous pores 13 (continuous ventilation holes) are formed in the microporous structure. The thin plate-shaped foamed metal electrode 10 (electrode 10 having a thickness dimension L1 of 0.05 mm to 0.5 mm (fuel electrode 18, air electrode 19, anode 31 and cathode 32)) is manufactured.

In the electrode manufacturing method, the permalloy fine powder 42 of Fe-Ni permalloy 41 is connected via a binder 43 by injection molding or extrusion molding, and the permalloy fine powder mixed molded product 46 (foam metal molding) produced by injection molding or extrusion molding. After degreasing the object), it is sintered (baked) at a predetermined temperature to obtain a thin plate-shaped foamed metal electrode 10 having a microporous structure having a large number of fine continuous pores 13 (continuous ventilation holes) (thickness dimension L1 is 0. Electrodes 10 of 05 mm to 0.5 mm (fuel electrode 18, air electrode 19, anode 31 and cathode 32) can be made, and the shape can be maintained with high strength, and when an impact is applied. Electrodes 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) capable of preventing damage or damage to the electrode 10 can be produced. The electrode manufacturing method has a thickness dimension L1 of 0.05 mm to 0.5 mm. Since the electrode 10 in the range can be formed, the electrode 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) having a small electric resistance and a smooth flow of current (excellent in proton conductivity) can be provided. Can be made.

The electrode manufacturing method includes the Fe content and the Ni content in the Fe-Ni permalloy 41 so that the work function of the permalloy fine powder 42 obtained by finely pulverizing the Fe-Ni permalloy 41 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 42 by finely pulverizing Fe-Ni permalloy 41 formed from Fe and Ni of content rate decided by content rate determination step A predetermined binder 43 and a predetermined pore-forming material 44 are added to the permalloy fine powder 42 prepared in the fine powder preparation step, and the binder 43 and the pore-forming material 44 are uniformly mixed and dispersed in the permalloy fine powder 42 to make the permalloy fine powder. Permalloy fine powder mixture preparation step of making a mixture 45 and permalloy fine powder mixture 45 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 46. The permalloy fine powder mixed molded product 46 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 46 is sintered at a predetermined temperature to obtain the permalloy fine powder 42. A large number of fine continuous pores 13 are uniformly and uniformly formed while being melt-bonded, and a thin plate-like foam having a microporous structure in which the open cells 13 are defined and surrounded by the permalloy melt in which the permalloy fine powder 42 is melt-bonded. Since the electrode 10 is manufactured by each step of the thin plate foam metal electrode making step of making the metal electrode 10, the thickness dimension L1 is in the range of 0.05 mm to 0.5 mm by these steps S1 to S5, and a large number of fine particles are produced. The electrode 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) (microporous structure thin plate-shaped foamed metal electrode) having continuous pores 13 (continuous ventilation holes) can be manufactured, and the electrode 10 (fuel electrode 10) can be manufactured. 18 and the air electrode 19, the anode 31 and the cathode 32) can be made at low cost.

The electrode manufacturing method can exhibit almost the same excellent catalytic activity (catalytic action) as an electrode carrying a platinum group element, and also has excellent catalytic activity (catalytic action) to sufficiently and reliably perform a catalytic function. Platinum group metal-free electrodes 10 (fuel electrode 18, air electrode 19, anode 31 and cathode 32) that can be used in the above can be prepared.

In the electrode manufacturing method, since the electrode 10 produced thereby exhibits excellent catalytic activity (cathodic action) substantially similar to that of an electrode carrying a platinum group element, sufficient electricity is generated in the polymer electrolyte fuel cell 17. Electrode 10 containing a small amount of platinum group metal (fuel electrode 18, air electrode 19, anode) capable of supplying sufficient electrical energy to the load 29 connected to the polymer electrolyte fuel cell 17. 31 and cathode 32) can be made. In the electrode manufacturing method, the electrode 10 (fuel electrode 18 and fuel electrode 18) containing a small amount of platinum group metal capable of efficiently performing electrolysis in the hydrogen gas generator 30 and generating a large amount of hydrogen gas in a short time. An air electrode 19, an anode 31 and a cathode 32) can be made.

10 Electrodes 11 Front surface 12 Rear surface 13 Continuous pores (continuous ventilation holes)
14 Ventilation port 15 Outer peripheral edge 16 Cell 17 Polymer electrolyte fuel cell 18 Fuel electrode (anode)
19 Air pole (cathode)
20 Solid polymer electrolyte membrane 21 Separator (bipolar plate)
22 Separator (bipolar plate)
23 Membrane / Electrode Assembly 24 Gas Diffusion Layer 25 Gas Diffusion Layer 26 Gas Seal 27 Gas Seal 28 Lead Wire 29 Load 30 Hydrogen Gas Generator 31 Anode (Anode)
32 Cathode
33 Solid polymer electrolyte film 34 Anode feeding member 35 Cathode feeding member 36 Anode water storage tank 37 Cathode water storage tank 38 Anode main electrode 39 Cathode main electrode 40 Membrane / electrode assembly 41 Fe-Ni Permalloy 42 Permalloy fine powder 43 Binder 44 Pore forming material (foaming agent)
45 Permalloy fine powder mixture 46 Permalloy fine powder mixed molding L1 Thickness dimension S1 Content rate determination step S2 Permalloy fine powder making step S3 Permalloy fine powder mixed making step S4 Permalloy fine powder mixed molding making step S5 Thin plate foam metal electrode making step

Claims (14)

In electrodes used as anodes or cathodes
In the electrode, a predetermined binder is uniformly mixed and dispersed in permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy, and a predetermined pore-forming material is uniformly mixed and dispersed, and the binder and the pores are uniformly mixed in the permalloy fine powder. The permalloy fine powder is formed by molding the permalloy fine powder mixture mixed with the forming material into a thin plate shape having a predetermined area, and then degreasing and sintering the permalloy fine powder mixed molded product formed into the thin plate shape having the predetermined area. 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 being melt-bonded, and has substantially the same catalytic activity as an electrode containing a platinum group element, and the open cells are the permalloy. An electrode characterized in that fine powder is defined by a melt-bonded permalloy melt. In the electrode, the content of Fe in the Fe-Ni permalloy and the content of Ni in the Fe-Ni permalloy are determined so that the work function of the permalloy fine powder is close to the work function of the platinum group element. The electrode according to claim 1. 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 electrode according to claim 1 or 2, which 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, and 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 electrode described. The electrode 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. The electrode 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. Claim 1 to claim that the Fe 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 electrode according to any one of Items 6. The electrode 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 foam density of the metal ^electrode, the electrode according to any claims 1 to 8 is in the range of ^{6.0g / cm 2 ~8.0g / cm 2} . The electrode 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. In an electrode manufacturing method for manufacturing an electrode used as an anode or a cathode,
In the electrode manufacturing method, the Fe content and the Ni content in the Fe-Ni permalloy are set so that the work function of the permalloy fine powder obtained by finely pulverizing Fe-Ni permalloy is close to the work function of the platinum group element. The content rate determination step to be determined, the permalloy fine powder preparation step of finely pulverizing Fe-Ni permalloy formed from Fe and Ni having the content rate determined by the content rate determination step to produce permalloy fine powder, and the permalloy fine powder. A predetermined binder and a predetermined pore-forming material are added to the permalloy fine powder prepared in the body preparation step, and the binder and the pore-forming material are uniformly mixed and dispersed in the permalloy fine powder to prepare a permalloy fine powder mixture. The permalloy fine powder mixture preparation step, the permalloy fine powder mixed product preparation step of molding the permalloy fine powder mixture prepared by the permalloy fine powder mixture preparation step into a thin plate shape to make a permalloy fine powder mixed molding, and the permalloy fine powder The permalloy fine powder mixed molded product prepared in the mixed molded product preparation step is degreased and the permalloy fine powder mixed molded product is sintered at a predetermined temperature, and the permalloy fine powder is melt-bonded and a large number of fine continuous pores are evenly formed. It is characterized by having a thin plate-shaped foamed metal electrode producing step of forming a thin plate-shaped foamed metal electrode having a microporous structure in which open cells are defined by a permalloy melt obtained by melt-bonding the permalloy fine powder. Electrode manufacturing method. The weight ratio determining step determines the Fe content in the Fe-Ni permalloy in the range of 45% to 55%, and the Ni content in the Fe-Ni permalloy in the range of 45% to 55%. The electrode manufacturing method according to claim 11, which is determined. The electrode manufacturing method according to claim 11 or 12, wherein the permalloy fine powder preparation step finely pulverizes the Fe-Ni permalloy to a particle size of 1 μm to 100 μm. The permalloy fine powder mixed molding preparation step is to mold the permalloy fine powder mixed by injection molding or extrusion molding, and the permalloy fine powder mixed molding having a thickness dimension of 0.05 mm to 0.5 mm and having a predetermined area and a thin plate shape. The electrode manufacturing method according to any one of claims 11 to 13 for making a product.

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