JP2010065283A - Catalyst layer paste composition, catalyst layer with transfer substrate, electrode of electrolytic cell for hydrogen generation and method for manufacturing the electrode, membrane catalyst layer assembly, electrolytic cell for hydrogen generation, and method for manufacturing the cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst layer paste composition for forming a catalyst layer substantially free of cracks or pinholes and excellent in stability, and to provide a catalyst layer with a transfer substrate using the composition, an electrode of an electrolytic cell for hydrogen generation and a method for manufacturing the electrode, a membrane catalyst layer joined body, an electrolytic cell for hydrogen generation, and a method for manufacturing the cell. <P>SOLUTION: The catalyst layer paste composition includes a catalyst powder, a binder, a solvent and water, to be used for an electrolytic cell for hydrogen generation, wherein the binder includes an anionic conductive polyelectrolyte. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a catalyst layer paste composition, a catalyst layer with a transfer substrate, an electrode for an electrolysis cell for hydrogen generation and a method for producing the same, and a membrane catalyst layer assembly, an electrolysis cell for hydrogen generation and a method for producing the same. Catalyst layer paste composition for generating hydrogen from an aqueous solution containing ammonia or nitrogen compound, catalyst layer with transfer substrate, electrode for electrolysis cell for hydrogen generation and method for producing the same, membrane catalyst layer assembly, and electricity for hydrogen generation The present invention relates to a decomposition cell and a manufacturing method thereof.

Hydrogen is widely used in various industrial fields including the oil refining and chemical industries. In particular, in recent years, hydrogen energy has attracted attention as a future energy, and research is being conducted focusing on fuel cells. However, it is known that hydrogen gas has a large volume per calorie and requires a large amount of energy for liquefaction, so that it is difficult to store or transport it as it is.
Accordingly, there has been a demand for the development of an efficient hydrogen supply method when it is necessary to supply hydrogen to a place where the fuel cell is used, such as when a fuel cell is used as a mobile body and a distributed power source such as a fuel cell vehicle. .

The current state of hydrogen supply methods will be described below.
First, a method of transporting and using hydrogen as a high-pressure gas can be mentioned. However, this method has problems in that it handles dangerous high-pressure gas, and it is difficult to miniaturize because the volume becomes excessive even at a considerably high pressure. On the other hand, a method of storing and transporting and using hydrogen as liquid hydrogen is also disclosed, but there is a problem that it is difficult to handle because it is an extremely low temperature of 20K (−253 ° C.).

  Next, a method for producing hydrogen in a place where hydrogen is used can be mentioned. A reforming method is known as such a method. The reforming method is widely performed by a known technique such as a steam reforming method of methane or light paraffin, an autothermal reforming method, or a partial oxidation method, but generally requires a high temperature of 700 ° C. or higher. Although reforming of methanol and dimethyl ether is a widely recognized method, it is usually carried out at a reaction temperature of 200 ° C. or higher. As described above, since the reforming method requires high temperature, it is difficult to reduce the size and improve the startability.

  In addition, a method of dehydrogenating hydrocarbons having a cyclohexane ring such as cyclohexane, methylcyclohexane, tetralin, decalin, etc., to obtain hydrogen has also been proposed, but this method also requires a relatively high temperature of 200 ° C.

  It is also effective to use hydrogen stored in the hydrogen storage alloy. However, the hydrogen storage amount is about 3% of the entire hydrogen storage alloy, and the weight is too high to be used for a moving body or the like.

On the other hand, a method of generating hydrogen by electrolysis of water has been conventionally known. Methods used for water electrolysis include alkaline electrolyte electrolysis that electrolyzes aqueous sodium hydroxide and potassium hydroxide, and solid polymer electrolysis using a fluorine ion exchange membrane ( For example, see Patent Documents 1 and 2.) According to these methods, hydrogen can be generated at room temperature and pressure by applying a voltage to the aqueous solution to be electrolyzed.
JP-A-8-314372 JP-A-8-269761

In the electrolysis cell by the above solid polymer electrolysis method, it is required that the catalyst layer is substantially free from cracks, pinholes, etc., and the catalyst layer paste is required to have dispersibility of the catalyst powder.
However, in the catalyst layer forming method described in Patent Document 2 using a paste comprising a catalyst and a polymer electrolyte, there remains a problem that a catalyst layer with good dispersibility cannot be formed and the catalyst layer may be cracked. ing.

  An object of the present invention is to provide a catalyst layer paste composition for forming a catalyst layer having substantially no cracks, pinholes, etc. and excellent stability, a catalyst layer with a transfer substrate using the same, and hydrogen generation It is an object to provide an electrode for an electrolysis cell and a production method thereof, a membrane catalyst layer assembly, an electrolysis cell for hydrogen generation, and a production method thereof.

  In order to achieve the above object, the invention according to claim 1 is a catalyst layer paste composition for use in an electrolysis cell for hydrogen generation, which contains catalyst powder, a binder, a solvent, and water, A catalyst layer paste composition comprising an anion conductive polymer electrolyte.

  The invention according to claim 2 is the catalyst layer paste composition according to claim 1, wherein the binder contains a non-anion conductive polymer.

  The invention described in claim 3 is a catalyst layer with a transfer substrate, characterized in that the catalyst layer paste composition according to claim 1 or 2 is formed on a transfer substrate.

  The invention according to claim 4 is a transfer substrate comprising a metal porous body formed on the catalyst layer paste composition of the catalyst layer with a transfer substrate according to claim 3. It is an attached electrode.

  The invention according to claim 5 is characterized in that the metal porous body is made of at least one selected from foamed nickel, foamed titanium and foamed silver. Electrode.

  The invention described in claim 6 is an electrode of an electrolysis cell for generating hydrogen, characterized in that the transfer substrate with the transfer substrate according to claim 4 or 5 is peeled off. .

  The invention according to claim 7 is an electrode of an electrolysis cell for hydrogen generation, characterized in that the catalyst layer paste composition according to claim 1 or 2 is formed on a metal porous body. is there.

  The invention according to claim 8 is the electricity for hydrogen generation according to claim 7, wherein the metal porous body is made of at least one selected from foamed nickel, foamed titanium, and foamed silver. It is an electrode of a decomposition cell.

  The invention according to claim 9 is a membrane / catalyst layer assembly comprising the catalyst layer paste composition according to claim 1 or 2 formed on both sides of an anion conductive polymer electrolyte membrane. It is.

  The invention according to claim 10 is an electrolysis cell for hydrogen generation, characterized in that the electrode according to any one of claims 6 to 8 is arranged on both surfaces of an anion conductive polymer electrolyte membrane. is there.

  An eleventh aspect of the invention is an electrolysis cell for hydrogen generation, characterized in that a metal porous body is disposed on both surfaces of the membrane-catalyst layer assembly according to the ninth aspect.

  The invention according to claim 12 is the electricity for hydrogen generation according to claim 11, wherein the metal porous body is made of at least one selected from foamed nickel, foamed titanium, and foamed silver. It is a decomposition cell.

  The invention according to claim 13 forms a catalyst layer paste composition by mixing and dispersing catalyst powder, a binder composed of at least an anion conducting polymer electrolyte, a solvent, and water in predetermined amounts, respectively. A step of applying and drying the catalyst layer paste composition onto a transfer substrate to form a catalyst layer with a transfer substrate, and forming the catalyst layer with a transfer substrate on the surface of the metal porous body. A method for producing an electrode for an electrolysis cell for hydrogen generation, comprising: a step of peeling the transfer substrate after bonding by pressure bonding.

  In the invention described in claim 14, a catalyst layer paste composition is formed by mixing and dispersing catalyst powder, a binder composed of at least an anion conductive polymer electrolyte, a solvent, and water in predetermined amounts. A step of coating and drying the catalyst layer paste composition on both sides of the anion conducting polymer electrolyte membrane to form a membrane catalyst layer assembly, and a metal porous body on both sides of the membrane catalyst layer assembly. And a step of bonding by pressure bonding. A method for producing an electrolysis cell for hydrogen generation.

  The invention according to claim 15 is to form a catalyst layer paste composition by mixing and dispersing catalyst powder, a binder composed of at least an anion conductive polymer electrolyte, a solvent, and water in predetermined amounts, respectively. A step of coating and drying the catalyst layer paste composition on a metal porous body to form an electrode, and the electrode so that the catalyst layer paste composition side is in contact with both surfaces of the anion conductive polymer electrolyte membrane. And a step of bonding by pressure bonding. A method for producing an electrolysis cell for hydrogen generation.

  The invention according to claim 16 forms a catalyst layer paste composition by mixing and dispersing catalyst powder, a binder composed of at least an anion conductive polymer electrolyte, a solvent, and water in predetermined amounts, respectively. A step of coating and drying the catalyst layer paste composition on a transfer substrate to form a catalyst layer with a transfer substrate, and the catalyst layer with a transfer substrate on both sides of the anion conductive polymer electrolyte membrane. The catalyst layer paste composition side is formed so as to be in contact with each other and bonded by pressure bonding, and then the transfer substrate is peeled to form a membrane catalyst layer assembly and metal porous on both surfaces of the membrane catalyst layer assembly A process for forming a body and joining them by pressure bonding.

  The invention according to claim 17 forms a catalyst layer paste composition by mixing and dispersing catalyst powder, a binder composed of at least an anion conductive polymer electrolyte, a solvent, and water in predetermined amounts, respectively. A step of applying and drying the catalyst layer paste composition onto a transfer substrate to form a catalyst layer with a transfer substrate, and forming the catalyst layer with a transfer substrate on the surface of the metal porous body. A step of forming an electrode by bonding by pressure bonding, and a step of forming the electrode so that the catalyst layer paste composition side is in contact with both surfaces of the anion conductive polymer electrolyte membrane and bonding by pressure bonding And a method for producing an electrolysis cell for hydrogen generation.

  According to the present invention, a catalyst layer paste composition for forming a catalyst layer that is substantially free of cracks, pinholes, etc. and has excellent stability, that is, good dispersibility of the catalyst, was used. It is possible to provide a catalyst layer with a transfer substrate, an electrode for an electrolysis cell for hydrogen generation and a method for producing the same, a membrane catalyst layer assembly, an electrolysis cell for hydrogen generation and a method for producing the same.

  Hereinafter, first to sixth embodiments of the present invention will be described with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, it should be noted that the drawings are schematic, differ from actual ones, and also include portions having different dimensional relationships and ratios between the drawings.

  Further, the following first to sixth embodiments exemplify apparatuses and methods for embodying the technical idea of the present invention, and the technical idea of the present invention is the component parts. The material, shape, structure, arrangement, etc. are not specified below. The technical idea of the present invention can be variously modified within the scope of the claims.

[First embodiment]
(Catalyst layer paste composition)
The catalyst layer paste composition according to the first embodiment of the present invention is a catalyst layer paste composition for use in an electrolysis cell for hydrogen generation, which contains catalyst powder, a binder, a solvent, and water. , Composed of an anion conductive polymer electrolyte.

(Catalyst powder)
The catalyst powder according to the present embodiment is made of catalyst metal fine particles, and known or commercially available products can be used.
Examples of the catalyst metal fine particles include Co, Ni, Pt, Ru, B, C, Mn, Fe, Pd, Rh, Li, Na, Mg, K, Ir, Nd, La, Ca, V, Ti, Cr, One kind or two or more kinds of metals selected from Cu, Zn, Al, Si, Mo, W, Ta, Zr, Hf, and Ag are exemplified, and the compound or an alloy thereof may be used.

  When the catalyst metal fine particles are an alloy composed of two or more kinds, platinum (Pt), iron (Fe), cobalt (Co), nickel (Ni), rhodium (Rh), ruthenium (Ru), iridium (Ir) Of these, alloy fine particles containing at least two kinds are preferred. For example, in addition to platinum-iron alloy, platinum-cobalt alloy, iron-cobalt alloy, cobalt-nickel alloy, iron-nickel alloy, iron-cobalt-nickel alloy can be used. Each ratio of these metals is not limited and can be appropriately selected from a wide range.

  The average particle diameter of the catalyst metal fine particles is not limited, but for example, colloidal particles of about 1 to 20 nm or powders of about 20 to 500 μm can be used.

  Specific examples of commercially available catalytic metal fine particles include nickel colloidal particles manufactured by Shinko Chemical Industry Co., Ltd., nickel-cobalt alloy particles (“NIA07PB”) manufactured by High Purity Chemical Laboratory.

  The catalyst metal fine particles may be supported on a carrier. The carrier on which the catalyst metal fine particles are supported is not limited, and a known or commercially available carrier can be used. For example, an alumina particle, a silica particle, a carbon particle etc. are mentioned suitably. From the viewpoint of good corrosion resistance and conductivity, carbon particles, particularly conductive carbon particles are preferred.

Examples of such conductive carbon particles include carbon black such as acetylene black, furnace black, channel black, ketjen black, graphite, activated carbon, and the like. These may be used alone or in combination of two or more. The specific surface area of the conductive carbon particles is not limited, but is usually about 10 to 1500 m ² / g, preferably about 10 to 500 m ² / g. The average particle diameter is generally about 0.01 to 1 μm, preferably about 0.01 to 0.2 μm, for example, as the average primary particle diameter.

  In the present embodiment, the carrier may be a fibrous material, in particular, a carbon fiber such as a vapor grown carbon fiber (VGCF), a carbon nanotube, or a carbon nanowire, in addition to the particulate material.

  The amount of the catalyst metal fine particles supported is appropriately determined depending on the types of the catalyst metal fine particles and the carrier, and is, for example, usually about 1 to 80 parts by mass, preferably about 3 to 50 parts by mass with respect to 100 parts by mass of the carrier. About a part.

  Specific examples of a catalyst that supports a commercially available catalyst include catalyst-supporting carbon (TEC10E50E, TEC35E51, etc.) manufactured by Tanaka Kikinzoku Co., Ltd., and HyperMec (registered trademark) manufactured by ACTA.

(binder)
The binder according to the present embodiment is made of an anion conductive polymer electrolyte. The anion conductive polymer electrolyte is not particularly limited as long as it is an electrolyte capable of conducting a hydroxide ion (OH ^- ion) as an anion, and a known or commercially available one can be used. For example, any polymer electrolyte of hydrocarbon type and fluororesin type can be used.

  Examples of the hydrocarbon-based polymer electrolyte include an electrolyte obtained by aminating a chloromethylated product of a copolymer of aromatic polyether sulfonic acid and aromatic polythioether sulfonic acid.

  Examples of the fluororesin-based polymer electrolyte include a polymer obtained by treating the terminal of a perfluorocarbon polymer having a sulfonic acid group with a diamine to be quaternized, or a polymer such as a quaternized product of polychloromethylsulfylene. Among these, a solvent-soluble one is particularly preferable.

As the electrolyte, for example, those disclosed in JP2003-86193A and JP2000-331693A may be used.
More specifically, chloromethylation is carried out by reacting a copolymer of aromatic polyether sulfonic acid and aromatic polythioether sulfonic acid with a chloromethylating agent. As the chloromethylating agent, for example, chloromethoxymethane, 1,4-bis (chloromethoxy) butane, 1-chloromethoxy-4-chlorobutane, formaldehyde-hydrogen chloride, paraformaldehyde-hydrogen chloride and the like can be used.

  The chloromethylated product thus obtained is reacted with an amine compound to introduce an anion exchange group. As the amine compound, for example, a monoamine, a polyamine compound having two or more amino groups in one molecule, and the like can be used. Specifically, in addition to ammonia, monoalkylamines such as methylamine, ethylamine, propylamine and butylamine, dialkylamines such as dimethylamine and diethylamine, aromatic amines such as aniline and N-methylaniline, pyrrolidine, piperazine and morpholine Monoamines such as heterocyclic amines, and polyamine compounds such as m-phenylenediamine, pyridazine, and pyrimidine can be used.

  The binder according to the present embodiment preferably contains a non-anion conductive polymer. Any non-anion conducting polymer may be used as long as it functions as a binder in forming the catalyst layer.

  Examples of non-anion conductive polymers include non-anion conductive fluororesins. By containing this fluororesin, the binding property of the catalyst layer components is improved, a stronger catalyst layer is formed, and water repellency can be imparted.

  Examples of the fluororesin include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, and the like. Among these, polytetrafluoroethylene is preferable from the viewpoint of better binding and water repellency.

  In addition to the non-anion conductive polymer, a conductive material may be added to the binder of the present embodiment. Similar to the non-anion conductive polymer, this conductive material only needs to function as a binder in forming the catalyst layer and have conductivity.

  Examples of the conductive material include the conductive carbon particles described above. In addition to the particulate matter described above, fibrous materials, particularly carbon fibers such as vapor grown carbon fibers (VGCF), carbon nanotubes, and carbon nanowires may be used. By containing this conductive material, the binding property of the catalyst layer components is improved, and a stronger catalyst layer can be formed.

  Thus, the binder which concerns on this Embodiment can use a non-anion conductive polymer and / or a conductive material suitably for an anion conductive polymer electrolyte further.

(solvent)
The solvent according to the present embodiment is not particularly limited, and is appropriately selected within a wide range. Examples thereof include various alcohols, various ethers, various dialkyl sulfoxides, water, or a mixture thereof. Among these solvents, alcohol is preferable. Examples of the alcohol include monohydric alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol, and polyhydric alcohols such as propylene glycol and diethylene glycol.

  By using the solvent in this Embodiment, the dispersibility of the catalyst powder in a catalyst layer paste composition can be made more favorable.

  In the catalyst layer paste composition of the present embodiment, the content (mass ratio) of the catalyst powder and the binder described above can be appropriately set according to the binder to be used. For example, when the binder is only an anion conductive polymer electrolyte, the anion conductive polymer electrolyte (solid content) is, for example, about 0.02 to 2 parts by mass with respect to 1 part by mass of the catalyst powder. When the binder further contains a non-anion conductive polymer (solid content), the content of the non-anion conductive polymer is usually about 0.01 to 0.3 mass per 1 part by mass of the catalyst powder. Part, preferably about 0.05 to 0.15 part by weight.

Further, the content (mass ratio) of the catalyst powder and the solvent is, for example, about 1 to 100 parts by mass, preferably about 3 to 80 parts by mass with respect to 1 part by mass of the catalyst powder.
And content (mass ratio) of catalyst powder and water is about 0.5-20 mass parts of water with respect to 1 mass part of catalyst powder, for example, Preferably, it is about 1-10 mass parts.

  The catalyst layer paste composition of the present embodiment can be produced by mixing and dispersing the above-described catalyst powder, binder, solvent, and water in predetermined amounts. The mixing order of the catalyst layer paste composition described above is not particularly limited. Known means can be widely used for mixing and dispersing. For example, ultrasonic dispersion, stirrer stirring, ball mill and the like can be mentioned.

According to the catalyst layer paste composition of the present embodiment, cracks, pinholes and the like are not substantially generated, and a catalyst layer having excellent stability, that is, good dispersibility of the catalyst can be formed.
Moreover, if the catalyst layer obtained by using the catalyst layer paste composition according to the present embodiment is used, it is possible to suppress the missing / peeling of the catalyst layer during electrolysis.
Moreover, according to this Embodiment, the film thickness adjustment of a catalyst layer becomes easy and a uniform catalyst layer can be formed easily. Thereby, the electrolysis cell for hydrogen generation excellent in hydrogen generation in durability can be provided.

[Second Embodiment]
(Catalyst layer with transfer substrate)
In the catalyst layer 7 with a transfer substrate according to the second embodiment of the present invention, as shown in FIG. 1, the catalyst layers 2 and 3 made of the catalyst layer paste composition described above are arranged on the transfer substrate 6. Is.

  The transfer substrate 6 is not particularly limited as long as it is in the form of a sheet or film, and examples thereof include a polymer film. In addition to the polymer film, art paper, coated paper, coated paper such as lightweight coated paper, non-coated paper such as notebook paper, copy paper, and the like may be used.

  As the material of the transfer substrate 6, in the case of a polymer film, polyimide, polyethylene terephthalate (PET), polyparvanic acid aramid, polyamide (nylon), polysulfone, polyethersulfone, polyphenylene sulfide, polyether etherketone, polyether Examples thereof include imide, polyarylate, and polyethylene naphthalate.

  Also, heat resistance of polyethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroperfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene (PTFE), etc. A fluororesin can also be used.

  The catalyst layer 7 with a transfer substrate according to the present embodiment is manufactured by forming the catalyst layer paste composition on one surface on the transfer substrate 6 and drying to form the catalyst layers 2 and 3. Can do.

  The thickness of the catalyst layers 2 and 3 may be appropriately determined in consideration of the type of electrode substrate, the thickness of the electrolyte membrane, etc., but is usually about 100 to 3000 μm, preferably about 300 to 2000 μm. Good.

  A method for forming the catalyst layer paste composition on the transfer substrate 6 is not particularly limited, and examples thereof include a knife coater, a bar coater, a spray, a dip coater, a spin coater, a roll coater, a die coater, and a curtain coater. General methods such as screen printing and rolling can be applied. In the case of thick coating, it is preferable to use a rolling method.

  In drying the paste composition, the drying temperature is usually about 40-100 ° C, preferably about 60-80 ° C. Although depending on the drying temperature, the drying time is usually about 5 minutes to 2 hours, preferably about 30 minutes to 1 hour.

  According to the present embodiment, it is possible to provide the catalyst layer 7 with a transfer substrate having a catalyst layer that is substantially free from cracks and pinholes and has excellent stability.

[Third embodiment]
(Electrode with transfer substrate)
As shown in FIG. 2, an electrode 7A with a transfer substrate according to a third embodiment of the present invention has metal porous bodies 4 and 5 on catalyst layers 2 and 3 of the catalyst layer 7 with transfer substrate. It is arranged. Since other configurations are the same as those of the second embodiment, description thereof will be omitted.

  As the metal porous bodies 4 and 5, the metal porous bodies 4 and 5 in the fourth embodiment to be described later may be used.

  The manufacturing method of the transfer substrate-attached electrode 7A according to the present embodiment is a method in which the metal porous bodies 4 and 5 are formed on the catalyst layers 2 and 3 of the transfer substrate-attached catalyst layer 7 by a second method. This is different from the manufacturing method according to the embodiment, and the others are the same as those of the second embodiment, and thus a duplicate description is omitted.

  In the manufacturing method of electrode 7A with transfer base according to the present embodiment, the catalyst layer with transfer base so that the catalyst layers 2 and 3 of catalyst layer 7 with transfer base face metal porous bodies 4 and 5, respectively. An electrode 7A with a transfer substrate can be manufactured by placing 7 on the surfaces of the metal porous bodies 4 and 5 and applying pressure and bonding.

  According to the present embodiment, it is possible to provide the transfer substrate-attached electrode 7A having a catalyst layer that is substantially free from cracks and pinholes and has excellent stability.

[Fourth embodiment]
(Electrode for electrolysis cell for hydrogen generation)
As shown in FIG. 3, an electrode 8 of an electrolysis cell for hydrogen generation according to a fourth embodiment of the present invention has a catalyst layer 2 made of the catalyst layer paste composition described above on the metal porous bodies 4 and 5. , 3 are arranged.

  The thicknesses of the porous metal bodies 4 and 5 according to the present embodiment are not limited, but are usually about 200 to 2000 μm, preferably about 300 to 600 μm.

   The nominal pore diameter (average pore diameter of the porous body) of the metal porous bodies 4 and 5 is not limited, but is usually about 30 to 700 μm, and preferably about 50 to 300 μm. Further, the porosity of the metal porous bodies 4 and 5 is not limited, and is, for example, about 75 to 98%, preferably about 80 to 95%.

  The material of the metal porous bodies 4 and 5 is not particularly limited as long as it is a porous body made of metal, and known or commercially available materials can be used. Specific examples include nickel foam, titanium foam, and silver foam. These may contain other components such as chromium, zirconia, molybdenum and tungsten. For example, the foamed nickel in the present embodiment includes chromium-containing foamed nickel and the like.

  The method for manufacturing the electrode 8 of the electrolysis cell for hydrogen generation according to the present embodiment can use the same method as in the second embodiment. That is, the catalyst layer paste composition can be formed on the metal porous bodies 4 and 5 and dried to form the catalyst layers 2 and 3 by the same method as in the second embodiment. . However, as a method of applying the catalyst layer paste composition to the metal porous bodies 4 and 5, since the surfaces of the metal porous bodies 4 and 5 are uneven and difficult to apply uniformly, a dipping method, brush coating, rolling method Etc. are preferred. More preferably, a rolling method is used.

  Moreover, the electrode 8 of the electrolysis cell for hydrogen generation which concerns on this Embodiment can also be manufactured by peeling the transfer base material 6 of the electrode 7A with a transfer base material in 3rd Embodiment.

  According to the present embodiment, it is possible to provide an electrode 8 of an electrolysis cell for hydrogen generation having a catalyst layer that is substantially free from cracks and pinholes and has excellent stability.

[Fifth embodiment]
(Membrane / catalyst layer assembly)
As shown in FIG. 4, the membrane-catalyst layer assembly 9 according to the fifth embodiment of the present invention is formed on both surfaces of an anion conductive polymer electrolyte membrane (hereinafter also referred to as “electrolyte membrane”) 1 as described above. The catalyst layers 2 and 3 made of the catalyst layer paste composition are disposed.

(Anion conductive polymer electrolyte membrane)
The anion conductive polymer electrolyte membrane 1 is not particularly limited as long as it contains the anion conductive polymer electrolyte, and a known or commercially available one can be used.

  The thickness of the anion conductive polymer electrolyte membrane 1 may be appropriately determined according to the thickness of the catalyst layers 2 and 3 and the like, but is usually about 10 to 300 μm, and preferably about 20 to 200 μm.

  The anion conductive polymer electrolyte membrane 1 may be composed of, for example, any one of hydrocarbon type and fluororesin type electrolytes. Examples of the hydrocarbon-based and fluororesin-based electrolytes are the same as those described above. If necessary, the electrolyte membrane 1 may be impregnated with a solvent such as an alkaline aqueous solution.

  When using a low concentration alkaline aqueous solution or when not using an alkaline aqueous solution, a hydrocarbon electrolyte membrane is preferred from the viewpoint of low cost.

  When the electrolyte membrane 1 is impregnated with a high concentration aqueous alkali solution, it is preferable to use a fluororesin-based electrolyte membrane from the viewpoint of alkali resistance. In addition, anion conductivity can be further improved by using a fluororesin electrolyte membrane.

  The alkaline aqueous solution may usually have a pH of about 9 to 14 for example. Specifically, for example, an aqueous KOH solution or an aqueous NaOH solution may be used. In the alkaline aqueous solution, for example, a monohydric alcohol such as methanol, ethanol or propanol; an alcohol such as a polyhydric alcohol such as ethylene glycol or propylene glycol can be mixed.

  The high concentration is appropriately changed depending on the type of the alkaline aqueous solution used, etc., but in the present embodiment, it means about 2 mol / liter or more, and the low concentration means less than about 2 mol / liter.

  The anion conductive polymer electrolyte membrane 1 according to the present embodiment may be formed by applying and drying a catalyst layer paste composition containing an anion conductive polymer electrolyte in a solvent. Further, a commercially available anion conductive polymer electrolyte membrane may be used as it is.

  Specific examples of commercially available fluororesin-based electrolyte membranes include Tosflex (registered trademark) IE-SF34 manufactured by Tosoh Corporation. Specific examples of the hydrocarbon-based electrolyte membrane include, for example, Aciplex (registered trademark) A-201, 211, 221 manufactured by Asahi Kasei Corporation; Neocepta (registered trademark) AM-1, AHA manufactured by Tokuyama Corporation Is mentioned.

  The manufacturing method of the membrane catalyst layer assembly 9 according to the present embodiment can use the same method as in the second embodiment. That is, the catalyst layer paste composition is formed on both surfaces of the anion conductive polymer electrolyte membrane 1 and dried to form the catalyst layers 2 and 3 in the same manner as in the second embodiment. Can do.

  According to the present embodiment, it is possible to provide the membrane-catalyst layer assembly 9 having a catalyst layer that is substantially free from cracks and pinholes and has excellent stability.

[Sixth embodiment]
(Electrolysis cell for hydrogen generation)
As shown in FIG. 5, an electrolysis cell 10 for hydrogen generation according to a sixth embodiment of the present invention has a fourth embodiment in which the anion conductive polymer electrolyte membrane 1 and the electrolyte membrane 1 are disposed on both surfaces. The electrode 8 of the electrolysis cell for hydrogen generation described in the embodiment, that is, the anode side and cathode side electrodes 12 and 13 is constituted. The anode side electrode 12 is composed of the anode side catalyst layer 2 and the anode side metal porous body 4, and the cathode side electrode 13 is composed of the cathode side catalyst layer 3 and the cathode side metal porous body 5.

  The shape of the electrolysis cell 10 for hydrogen generation is not limited, and may be a flat plate type or a cylindrical type. Examples of the shape of the flat plate include a flat plate and a flat plate corrugated integrated type obtained by bending a flat plate into a waveform. Examples of the cylindrical shape include a cylindrical shape or a truncated cone shape in which a flat plate shape is formed in a cylindrical shape, or a cylindrical corrugated shape shape having a waveform shape in the circumferential direction. In addition, a honeycomb type in which the inside of the cylindrical shape has a honeycomb structure can also be exemplified.

(fuel)
The hydrogen generation electrolysis cell 10 according to the present embodiment generates hydrogen by supplying liquid fuel or the like, as will be described later.

  Examples of the liquid fuel include water and an ionic aqueous solution on the cathode side electrode 13 side. Preferably, water is used. Examples of the anode side electrode 12 include an aqueous solution containing ammonia or a nitrogen-containing compound. Specific examples of nitrogen-containing compounds include amines such as dimethylamine, trimethylamine, ethylamine, isopropylamine, butylamine, phenylamine, and amylamine, or amines such as trimethylamine, ethylamine, isopropylamine, butylamine, phenylamine, and amylamine, Furthermore, hydrazine, indole, pyridine, nicotinic acid, caffeic acid, sulfanilic acid, sulfanilamide and the like can be mentioned, and an aqueous solution in which these are mixed can also be mentioned. Preferably, an aqueous ammonia solution is used.

  An aqueous alkaline solution can be added to the liquid fuel as necessary. When adding an aqueous alkali solution, it may be added so that the pH after the addition is usually about 9 to 14. Specifically, as such an alkaline aqueous solution, a KOH solution, an NaOH solution, or the like may be used.

  When using the electrolysis cell 10 for generating hydrogen according to the present embodiment, liquid fuel is used as the fuel. Therefore, a fuel suction material may be further disposed as necessary. The fuel suction material is disposed on the surface side of the metal porous bodies 4 and 5 in contact with the liquid fuel. Thereby, fuel can be efficiently supplied to the metal porous bodies 4 and 5. Examples of the material for the fuel suction material include urethane foam and polypropylene foam.

(Middle layer)
In the present embodiment, an intermediate layer is formed (laminated) between the anode side catalyst layer 2 and the anode side metal porous body 4 and / or between the cathode side catalyst layer 3 and the cathode side metal porous body 5. You may do it. In addition, an intermediate layer may be formed between the anode side catalyst layer 2 and the electrolyte membrane 1 and / or between the cathode side catalyst layer 3 and the electrolyte membrane 1. The intermediate layer may be formed by combining the above arrangements, and the number thereof is not limited, and may be only one layer or a plurality of layers.

  The intermediate layer is preferably a porous body containing a conductive material. The porosity of the porous body is, for example, about 10 to 80%, preferably about 30 to 70%. The film thickness of the intermediate layer is not limited, and is, for example, about 0.5 to 50 μm, preferably about 1 to 20 μm, and more preferably about 1 to 10 μm.

  The material of the intermediate layer is not particularly limited, but from the viewpoint of conductivity, for example, metals such as iron, cobalt, nickel, palladium, silver, ruthenium, iridium, molybdenum, manganese, or alloys thereof, conductive carbon Materials are preferred. The intermediate layer may be made of the same material as the catalyst layers 2 and 3.

  When the intermediate layer is a metal, nickel, silver, and the like are particularly preferable among the above from the viewpoint of excellent catalytic activity. When the intermediate layer is a conductive carbon material, from the viewpoint of excellent gas diffusion and conductivity, carbon black such as acetylene black, furnace black, channel black, ketjen black, graphite, activated carbon, carbon fiber, carbon Preferred examples include nanotubes and carbon nanowires.

  The intermediate layer may be imparted with hydrophilicity or water repellency, if necessary, depending on the method of using the electrolysis cell for generating hydrogen. The material having hydrophilicity or water repellency can be widely selected from known or commercially available materials.

  By disposing the intermediate layer, the fuel liquid introduced into the electrolysis cell 10 can be more easily penetrated into the catalyst layers 2 and 3 and the electrolyte membrane 1 and the catalyst layers 2 and 3 and the metal porous body. Since the contact resistance with 4, 5, etc. can be reduced, the electrolysis performance can be further improved.

(Hydrogen generation method)
As shown in FIG. 6, the hydrogen generation electrolysis cell 10 according to the present embodiment applies an external voltage (for example, about 500 mV) via an external circuit 11 in which an anode side electrode 12 and a cathode side electrode 13 are connected. By applying, electrolysis of ammonia and water is performed, thereby generating hydrogen. These will be described in detail below.

First, for example, an aqueous ammonia solution is supplied as fuel to the anode-side catalyst layer 2 through the anode-side metal porous body 4, and water is supplied to the cathode-side catalyst layer 3 through the cathode-side metal porous body 5. (H ₂ O) is supplied. In the anode side electrode 12, hydroxide ions (OH ⁻ ) that have passed through the anion conductive polymer electrolyte membrane 1 react with ammonia (NH ₃ ) in the aqueous ammonia solution to react with nitrogen (N ₂ ), water, and electrons ( e ⁻ ) is generated, and the oxidation reaction of the formula (1) proceeds.
Anode side: 2NH ₃ + 6OH ⁻ → N ₂ + 6H ₂ O + 6e ⁻ (1)

In the cathode-side electrode 13, the supplied water reacts with the electrons that have reached through the external circuit 11 to generate hydrogen (H ₂ ) and hydroxide ions, and the reduction reaction of formula (2) proceeds. .
Cathode side: 6H ₂ O + 6e ⁻ → 3H ₂ + 6OH ⁻ (2)

The generated hydroxide ions are supplied from the cathode side electrode 13 side to the anode side electrode 12 side through the anion conductive polymer electrolyte membrane 1. As a whole, the electrolysis reaction of the formula (3) in which ammonia is oxidized to generate nitrogen and hydrogen proceeds to generate hydrogen.
Electrolysis _{reaction: 2NH 3 → N 2 + 3H} 2 ... (3)

  Nitrogen and water generated on the anode side electrode 12 side are discharged to the outside together with the remaining aqueous ammonia solution. The hydrogen generated on the cathode side electrode 13 side is discharged to the outside together with the remaining water and collected.

(Method for producing electrolysis cell for hydrogen generation)
First, a catalyst layer paste composition is produced by the same method as in the first embodiment. Next, the catalyst layers 2 and 3 and the metal porous bodies 4 and 5 made of the catalyst layer paste composition are formed on the surface of the anion conductive polymer electrolyte membrane 1. Examples of these forming methods include the following methods.
(I) As shown in FIG. 7 (a), the catalyst layer paste composition was directly applied to both surfaces of the anion conductive polymer electrolyte membrane 1 by the method shown in the fifth embodiment and dried to form a catalyst. A method of laminating metal porous bodies 4 and 5 on both sides of the membrane catalyst layer assembly 9 after forming the layers 2 and 3 to produce the membrane catalyst layer assembly 9;
(Ii) As shown in FIG. 7B, the metal porous bodies 4 and 5 are formed with the catalyst layers 2 and 3 made of the catalyst layer paste composition by the method shown in the fourth embodiment. A method of directly laminating the electrode 8 on both sides of the anion conductive polymer electrolyte membrane 1 after the electrode 8 is produced;
(Iii) As shown in FIG. 7C, the catalyst layer paste composition was applied to the transfer substrate 6 and dried to form the catalyst layers 2 and 3 by the method shown in the second embodiment. After obtaining the catalyst layer 7 with the transfer substrate, the catalyst layer 7 with the transfer substrate is placed on the surface of the electrolyte membrane 1 so that the catalyst layers 2 and 3 of the obtained catalyst layer 7 with the transfer substrate face the electrolyte membrane 1. After placing and pressurizing and joining the transfer base material 6 to produce the membrane catalyst layer assembly 9, the metal porous body 4 is formed on the catalyst layers 2 and 3 of the membrane catalyst layer assembly 9. A method of laminating 5 respectively.
(Vi) As shown in FIG. 7 (d), the catalyst layer paste composition is applied to the transfer substrate 6 by the method shown in the second and third embodiments and dried to form catalyst layers 2 and 3. After obtaining the catalyst layer 7 with the transfer substrate having formed thereon, the transfer group is formed so that the catalyst layers 2 and 3 of the obtained catalyst layer 7 with the transfer substrate face one side surface of the metal porous bodies 4 and 5. The material-attached catalyst layer 7 is placed on the surfaces of the metal porous bodies 4 and 5 and pressed and joined to produce an electrode 7A with a transfer substrate. Next, after the transfer substrate 6 of the electrode 7A with the transfer substrate is peeled to produce the electrode 8, the electrode 8 is laminated so that the catalyst layers 2 and 3 are in contact with both surfaces of the anion conductive polymer electrolyte membrane 1 .
7A to 7D show a method of forming each layer on one side surface of the anion conductive polymer electrolyte membrane 1 for convenience.

  After forming the electrodes 8 (12, 13) composed of the catalyst layers 2 and 3 and the metal porous bodies 4 and 5 on both surfaces of the anion conductive polymer electrolyte membrane 1 by the method described above, as shown in FIG. The upper surfaces of the electrodes 8 (12, 13) are pressurized so that the catalyst layers 2, 3 and the electrolyte membrane 1 are in contact with each other. Pressurization is usually about 0.1 to 15 MPa, preferably about 0.5 to 10 MPa. In addition, it is preferable to heat the pressure surface during pressurization. The temperature of the heating surface is usually about 20 to 100 ° C., preferably about 30 to 85 ° C., in order to avoid breakage, modification and the like of the electrolyte membrane 1. In this way, the anion conducting polymer electrolyte membrane 1 and the electrodes 12 and 13 are joined by pressure bonding, whereby the hydrogen generating electrolysis cell 10 shown in FIG. 5 can be manufactured.

  According to the present embodiment, there is provided a hydrogen generation electrolysis cell 10 that can exhibit excellent hydrogen generation performance because it has a catalyst layer that is substantially free of cracks and pinholes and has excellent stability. Can do.

  Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples, and various modifications can be made without departing from the scope of the present invention.

[Example 1] (Electrode)
By performing a copolymer of aromatic polyether sulfonic acid and aromatic polythioether sulfonic acid sequence chloromethylated and aminated anion ^- was obtained (OH ion) conductive polymer electrolyte. This was added to a solvent (tetrahydrofuran) to obtain 100 g of a 5% by mass anion conductive polymer electrolyte solution.

  Nickel-cobalt alloy particles (High Purity Chemical Laboratory, “NIA07PB”) and the 5% by mass anionic conductive polymer electrolyte solution (solid content) obtained above are in a mass ratio of 1: 0.1. A paste composition for forming a catalyst layer is prepared by mixing 10 g of nickel-cobalt alloy particles and 20 g of a 5% by mass anion conductive polymer electrolyte solution and adding the mixture to 30 g of water, 50 g of ethanol and 50 g of isopropyl alcohol. did.

A porous metal sheet-like foamed nickel (Mitsubishi Materials Corp., thickness 500 μm, nominal diameter 150 μm, porosity 85%) is used as an electrode substrate, and after the catalyst layer forming paste composition is dried by a rolling method, After coating so that the mass of nickel-cobalt was about 4 mg / cm ² , it was dried at about 85 ° C. for about 15 minutes to produce a total of two electrodes, an anode side electrode 12 and a cathode side electrode 13.

[Example 2] (Electrode)
Nickel-cobalt alloy particles (High Purity Chemical Laboratory, “NIA07PB”), anionic conductive polymer electrolyte solution (solid content), and non-anionic conductive polymer (solid content) are in a mass ratio of 2: 0.2: 10 g of nickel-cobalt alloy particles and 20 g of the 5% by mass anion conductive polymer electrolyte solution obtained above were mixed so as to be 0.3, and this was mixed with 30 g of water and 50 g of ethanol, 50 g of isopropyl alcohol, 60% by mass. A catalyst layer forming paste composition was prepared by adding 2.5 g of a polytetrafluoroethylene solution (PTFE dispersion: manufactured by Aldrich).

As in Example 1, a metal porous sheet-like foamed nickel (Mitsubishi Materials Co., Ltd., thickness: 500 μm, nominal diameter: 150 μm, porosity: 85%) was used as the electrode substrate, and the catalyst layer was formed thereon by rolling. The paste composition for coating was applied so that the mass of nickel-cobalt after drying was about 4 mg / cm ^2, and then dried at about 85 ° C. for about 15 minutes to obtain a total of 2 anode side electrodes 12 and cathode side electrodes 13. Sheet electrodes were produced.

[Example 3] (Catalyst layer with transfer substrate)
Using a PET film (E3120, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a transfer substrate, the catalyst layer paste composition prepared in Example 1 is formed on one side with a doctor blade. The catalyst layer forming paste composition was applied so that the nickel-cobalt mass after drying was about 4 mg / cm ^2, and then dried at about 85 ° C. for about 15 minutes, whereby catalyst layer 7 with a transfer substrate (cathode) 2 sheets in total for the catalyst layer and the anode catalyst layer) were produced.

[Example 4] (Catalyst layer with transfer substrate)
Using a PET film (E3120, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a transfer substrate, the catalyst layer paste composition prepared in Example 2 is formed on one side with a doctor blade. The catalyst layer forming paste composition was applied so that the nickel-cobalt mass after drying was about 4 mg / cm ^2, and then dried at about 85 ° C. for about 15 minutes, whereby catalyst layer 7 with a transfer substrate (cathode) 2 sheets in total for the catalyst layer and the anode catalyst layer) were produced.

Example 5 (Electrode)
A paste composition for forming a catalyst layer was prepared in the same manner as in Example 1 except that platinum powder (Pure Chemical Laboratory, “PTE02PB”) was used as the catalyst powder.
In the same manner as in Example 1, a metal porous sheet-like foamed nickel (Mitsubishi Materials Co., Ltd., thickness: 500 μm, nominal diameter: 150 μm, porosity: 85%) was used as the electrode substrate, and the catalyst layer was formed by spraying on this The paste composition for coating was applied so that the weight of platinum after drying was about 1 mg / cm ^2, and then dried at about 85 ° C. for about 15 minutes, whereby a total of two sheets of anode side electrode 12 and cathode side electrode 13 were obtained. An electrode was produced.

[Comparative Example 1] (Electrode)
A paste composition for forming a catalyst layer was prepared by mixing 10 g of nickel-cobalt alloy particles (High Purity Chemical Laboratory, "NIA07PB"), 30 g of water, 50 g of ethanol, and 50 g of isopropyl alcohol.

As in Example 1, a metal porous sheet-like foamed nickel (Mitsubishi Materials Co., Ltd., thickness: 500 μm, nominal diameter: 150 μm, porosity: 85%) was used as the electrode substrate, and the catalyst layer was formed thereon by rolling. After coating the paste composition for drying so that the mass of nickel-cobalt after drying was 4 mg / cm ² , it was dried at about 85 ° C. for about 15 minutes to obtain a total of two sheets of anode side electrode 12 and cathode side electrode 13 An electrode was prepared.

(Evaluation Test 1)
The performance of the electrodes prepared in Examples 1 to 5 and Comparative Example 1 and the catalyst layer with a transfer substrate was examined by the following method. That is, each electrode and a catalyst layer with a transfer substrate were cut into a size of 10 cm × 10 cm, and the surface thereof was observed with a digital microscope (manufactured by Keyence Corporation, VH-8000) at 50 times and 300 times. The presence or absence of holes was confirmed visually.

  As a result, no pinholes occurred on the surfaces of Examples 1 to 5, and no catalyst layer was observed. On the other hand, many pinholes and cracks were generated on the surface of Comparative Example 1, and the catalyst layer was missing at this point.

(Evaluation test 2)
The catalyst layers of the electrodes and the catalyst layer with the transfer base material obtained in Examples 1 to 5 and Comparative Example 1 were subjected to thermocompression using a hot press machine at a temperature of about 80 ° C., a press pressure of about 3 MPa, for about 3 minutes. The conductive polymer electrolyte membrane 1 (Asaplex A-221 manufactured by Asahi Kasei Co., Ltd., thickness 150 μm) was bonded and transferred to produce an electrolysis cell 10 for hydrogen generation.

  The layer configurations of Examples 1, 2 and 5 and Comparative Example 1 after hot pressing were metal porous body / catalyst layer / electrolyte membrane / catalyst layer / metal porous body, and the layer configurations of Examples 3 and 4 were It becomes transfer substrate / catalyst layer / electrolyte membrane / catalyst layer / transfer substrate. In Examples 3 and 4, after the transfer substrate was peeled off, a metal porous body was placed on each catalyst layer, and again subjected to thermocompression bonding at a pressure of about 1 MPa and a temperature of about 80 ° C. for about 3 minutes.

  The hydrogen generation electrolysis cell 10 produced above was subjected to a hydrogen generation test by supplying water to the cathode side and 1M aqueous ammonia solution + 5M KOH to the anode side as liquid fuel.

  As a result, the hydrogen generation electrolysis cell 10 using the electrodes obtained in Examples 1 to 5 was gas chromatographed after 1 hour and 10 hours in a hydrogen generation durability test in which hydrogen was continuously generated. Hydrogen generation could be confirmed by measurement using Shimadzu Corporation. Furthermore, the lack of a catalyst layer of the electrode was not observed visually.

  On the other hand, in the hydrogen generation electrolysis cell 10 using the electrode of Comparative Example 1, hydrogen generation was not confirmed after 1 hour in the hydrogen generation durability test, and the catalyst layer of the electrode was visually anion conductive polymer. It was confirmed that it was missing from the electrolyte membrane.

  From the above, the electrolysis cell for hydrogen generation 10 using the catalyst layer paste composition according to the present invention is excellent in hydrogen generation capacity and the like, and is substantially free from cracks and pinholes and has excellent stability. It was found that a layer was formed.

The typical sectional view of the catalyst layer with a transfer substrate concerning a 2nd embodiment of the present invention. The typical sectional view of the electrode with a transfer substrate concerning a 3rd embodiment of the present invention. The typical sectional view of the electrode of the electrolysis cell for hydrogen generation concerning the 4th embodiment of the present invention. The typical sectional view of the membrane catalyst layer zygote concerning the 5th embodiment of the present invention. The typical sectional view of the electrolysis cell for hydrogen generation concerning the 6th embodiment of the present invention. The figure explaining operation | movement of the electrolysis cell for hydrogen generation which concerns on the 6th Embodiment of this invention. It is explanatory drawing of the method of forming an electrode in an anion conductive solid polymer electrolyte membrane, Comprising: (a) After apply | coating and drying a catalyst layer paste composition directly on an anion conductive polymer electrolyte membrane, a metal porous body is formed. A layering method, (b) a method of directly stacking electrodes of an electrolysis cell for hydrogen generation on an anion conductive polymer electrolyte membrane, and (c) forming a catalyst layer with a transfer substrate on the anion conductive polymer electrolyte membrane. The method which shows the method and (d) peeling the transfer base material of an electrode with a transfer base material to make an electrode, and forming this electrode in an anion conductive polymer electrolyte membrane. It is explanatory drawing of the manufacturing method of the electrolysis cell for hydrogen generation which concerns on the 6th Embodiment of this invention, Comprising: The electrode of the electrolysis cell for hydrogen generation is crimped | bonded to both surfaces of the anion conductive solid polymer electrolyte membrane. Process drawing to form.

Explanation of symbols

1 ... anion conductive polymer electrolyte membrane 2 ... catalyst layer (anode side)
3 ... Catalyst layer (cathode side)
4 ... Metal porous body (anode side)
5 ... Metal porous body (cathode side)
6 ... Transfer base material 7 ... Catalyst layer 7A with transfer base material ... Electrode with transfer base material 8 ... Electrode of electrolysis cell for hydrogen generation (12: anode side, 13: cathode side)
9 ... Membrane / catalyst layer assembly 10 ... Electrolysis cell 11 for hydrogen generation ... External circuit

Claims (17)

A catalyst layer paste composition for use in an electrolysis cell for hydrogen generation, containing catalyst powder, a binder, a solvent, and water,
The catalyst layer paste composition, wherein the binder is composed of an anion conductive polymer electrolyte.   The catalyst layer paste composition according to claim 1, wherein the binder contains a non-anion conductive polymer.   A catalyst layer with a transfer substrate, comprising the catalyst layer paste composition according to claim 1 or 2 formed on a transfer substrate.   An electrode with a transfer substrate, comprising a metal porous body formed on the catalyst layer paste composition of the catalyst layer with a transfer substrate according to claim 3.   The electrode with a transfer substrate according to claim 4, wherein the metal porous body is made of at least one selected from foamed nickel, foamed titanium, and foamed silver.   6. An electrode for an electrolysis cell for hydrogen generation, wherein the transfer substrate of the electrode with transfer substrate according to claim 4 or 5 is peeled off.   An electrode of an electrolysis cell for hydrogen generation, wherein the catalyst layer paste composition according to claim 1 or 2 is formed on a metal porous body.   The electrode of the electrolysis cell for hydrogen generation according to claim 7, wherein the metal porous body is made of at least one selected from foamed nickel, foamed titanium, and foamed silver.   3. A membrane / catalyst layer assembly comprising the catalyst layer paste composition according to claim 1 or 2 formed on both sides of an anion conductive polymer electrolyte membrane.   An electrolysis cell for hydrogen generation, wherein the electrode according to any one of claims 6 to 8 is disposed on both sides of an anion conductive polymer electrolyte membrane.   An electrolysis cell for hydrogen generation, wherein a metal porous body is disposed on both surfaces of the membrane-catalyst layer assembly according to claim 9.   12. The electrolysis cell for hydrogen generation according to claim 11, wherein the metal porous body is made of at least one selected from foamed nickel, foamed titanium, and foamed silver. A step of mixing and dispersing catalyst powder, at least a binder composed of an anion-conducting polymer electrolyte, a solvent, and water in respective predetermined amounts to form a catalyst layer paste composition;
Applying the catalyst layer paste composition onto a transfer substrate and drying to form a catalyst layer with a transfer substrate; and
An electrode of an electrolysis cell for hydrogen generation comprising: a step of forming the catalyst layer with a transfer substrate on the surface of a metal porous body, bonding the substrate by pressure bonding, and then peeling the transfer substrate. Manufacturing method. A step of mixing and dispersing catalyst powder, at least a binder composed of an anion-conducting polymer electrolyte, a solvent, and water in respective predetermined amounts to form a catalyst layer paste composition;
Applying the catalyst layer paste composition to both sides of the anion conductive polymer electrolyte membrane and drying to form a membrane catalyst layer assembly;
Forming a metal porous body on both surfaces of the membrane-catalyst layer assembly and bonding them by pressure bonding. A method for producing an electrolysis cell for hydrogen generation, comprising: A step of mixing and dispersing catalyst powder, at least a binder composed of an anion-conducting polymer electrolyte, a solvent, and water in respective predetermined amounts to form a catalyst layer paste composition;
Applying the catalyst layer paste composition to a metal porous body and drying to form an electrode;
A process for producing an electrolysis cell for hydrogen generation, comprising: forming the electrode on both surfaces of an anion conductive polymer electrolyte membrane so that the catalyst layer paste composition side is in contact with the electrode layer, and bonding them by pressure bonding. A step of mixing and dispersing catalyst powder, at least a binder composed of an anion-conducting polymer electrolyte, a solvent, and water in respective predetermined amounts to form a catalyst layer paste composition;
Applying the catalyst layer paste composition onto a transfer substrate and drying to form a catalyst layer with a transfer substrate; and
The catalyst layer with the transfer substrate is formed so that the catalyst layer paste composition side is in contact with both surfaces of the anion conductive polymer electrolyte membrane and bonded by pressure bonding, and then the transfer substrate is peeled off to bond the membrane catalyst layer. A method for producing an electrolysis cell for hydrogen generation, comprising: forming a body; and forming a metal porous body on both surfaces of the membrane-catalyst layer assembly and bonding them by pressure bonding. A step of mixing and dispersing catalyst powder, at least a binder composed of an anion-conducting polymer electrolyte, a solvent, and water in respective predetermined amounts to form a catalyst layer paste composition;
Applying the catalyst layer paste composition onto a transfer substrate and drying to form a catalyst layer with a transfer substrate; and
Forming an electrode by forming the catalyst layer with the transfer substrate on the surface of the metal porous body and bonding it by pressure bonding; and
A process for producing an electrolysis cell for hydrogen generation, comprising: forming the electrode on both surfaces of an anion conductive polymer electrolyte membrane so that the catalyst layer paste composition side is in contact with the electrode layer, and bonding them by pressure bonding.

Images