JP2010040515A - Electrolyte membrane for solid alkali type fuel cell, electrolyte membrane-catalyst layer assembly for solid alkali type fuel cell, electrolyte membrane-electrode assembly for solid alkali type fuel cell, and solid alkali type fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolyte membrane for a solid alkali type fuel cell, an electrolyte membrane-catalyst layer assembly for a solid alkali type fuel cell, an electrolyte membrane-electrode assembly for a solid alkali type fuel cell and a solid alkali type fuel cell, with influence of swelling or contraction of the electrolyte membrane alleviated with the use of an anion conductive solid polymer electrolyte membrane for an electrolyte membrane as well as a frame-shaped gasket for disposing the catalyst layer on the electrolyte membrane, capable of forming a catalyst layer of a desired shape, and excellent in mass production. <P>SOLUTION: The electrolyte membrane 10 for a solid alkali type fuel cell is provided with an anion conductive solid polymer electrolyte membrane 1, and a frame-shaped gasket 2 having an alkali-proof adhesion layer 3 on one surface and an opening 4 for arranging a catalyst layer at its center. The gasket 2 is arranged on one surface of the anion conductive solid polymer electrolyte membrane 1 through the adhesion layer 3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrolyte membrane for a solid alkaline fuel cell, an electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell, an electrolyte membrane-electrode assembly for a solid alkaline fuel cell, and a solid alkaline fuel cell.

  In recent years, fuel cells are considered promising as one of the next generation energy systems. There are various types of fuel cells, such as alkaline fuel cells, phosphoric acid fuel cells, polymer electrolyte fuel cells, solid oxide fuel cells, and molten carbonate fuel cells. It has characteristics. Among them, the polymer electrolyte fuel cell has a low operating temperature and a low electrolyte resistance, and also uses a highly active catalyst, so it can obtain a high output even in a small size. Therefore, development for early commercialization of home cogeneration systems and the like is underway.

Conventionally, a polymer electrolyte fuel cell uses a cation (H ⁺ ) conductive polymer electrolyte membrane as an electrolyte membrane, and has a structure in which a catalyst layer and an electrode base material are laminated on both sides and sandwiched between separators. A polymer electrolyte fuel cell is well known. In the cation conductive polymer electrolyte fuel cell, a method of directly applying a catalyst paste to an electrolyte membrane is disclosed for forming a catalyst layer on the electrolyte membrane. (For example, refer to Patent Document 1).

  However, the cation conductive polymer electrolyte membrane has a problem that it is swollen by a solvent component contained in the catalyst paste and contracts by drying. Furthermore, there is a problem that it is difficult to form a catalyst layer having a desired shape on the electrolyte membrane by swelling.

On the other hand, in recent years, an anion-conducting solid polymer fuel cell (also called a solid alkaline fuel cell) using an anion-conducting solid polymer electrolyte membrane that allows anion (OH ⁻ ) to pass therethrough as the polymer electrolyte membrane has been called. ) Is attracting attention. For example, a solid alkaline fuel cell using a fluorine-based anion exchange membrane as an anion conductive solid polymer electrolyte membrane has been disclosed (for example, see Patent Document 2).

JP 2006-120433 A JP 2006-244961 A

  Compared with a cation conductive solid polymer electrolyte membrane, an anion conductive solid polymer electrolyte membrane is generally less likely to swell or shrink due to drying as described above, and can be directly applied to the electrolyte membrane. However, due to the dispersion of the catalyst metal particles and the ion conductive electrolyte contained in the catalyst forming paste, there is a problem that the viscosity of the catalyst layer forming paste tends to be low, and the shape cannot be maintained when the catalyst layer is formed. . Further, the electrode end face has a problem in that the catalyst layer is peeled off due to the sagging of the paste for forming the catalyst layer with reduced viscosity. On the other hand, when the viscosity is increased, the shape can be maintained, but there are problems that formation of the catalyst layer is difficult and cracking of the catalyst layer is likely to occur.

  The object of the present invention is to use an anion conductive solid polymer electrolyte membrane for the electrolyte membrane, and to use a frame-shaped gasket for arranging the catalyst layer on the electrolyte membrane, thereby reducing the influence of swelling and shrinkage of the electrolyte membrane. In addition, an electrolyte membrane for a solid alkaline fuel cell, an electrolyte membrane for a solid alkaline fuel cell-catalyst layer assembly, and a solid alkaline fuel cell that can form a catalyst layer in a desired shape and have excellent mass productivity An electrolyte membrane-electrode assembly for use and a solid alkaline fuel cell are provided.

  In order to achieve the above object, an invention according to claim 1 is provided with an anion conductive solid polymer electrolyte membrane, an alkali-resistant adhesive layer on one surface, and an opening for disposing a catalyst layer in the center. A gasket having a frame shape, and the gasket is disposed on one surface of the anion conductive solid polymer electrolyte membrane via the adhesive layer, for a solid alkaline fuel cell It is an electrolyte membrane.

  The invention according to claim 2 is characterized in that the gasket is further disposed on the other surface of the anion conductive solid polymer electrolyte membrane via the adhesive layer. It is an electrolyte membrane for solid alkaline fuel cells.

  The invention according to claim 3 is disposed on the surface of the electrolyte membrane for a solid alkaline fuel cell according to claim 1 and the anion conductive solid polymer electrolyte membrane and in the region of the opening. An electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell, comprising: a catalyst layer.

  According to a fourth aspect of the present invention, there is provided the electrolyte membrane for a solid alkaline fuel cell according to the second aspect and each region of the opening on each surface of the anion conductive solid polymer electrolyte membrane. An electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell, comprising: a catalyst layer disposed therein.

  The invention according to claim 5 is the electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell according to claim 3 or 4, wherein the catalyst layer has a thickness smaller than that of the gasket. It is.

  In the invention according to claim 6, the gasket further covers an outer end face of the anion conductive solid polymer electrolyte membrane, and the adhesive layer is located outside the anion conductive solid polymer electrolyte membrane. The electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell according to claim 4 or 5, wherein the two are bonded together.

  The invention according to claim 7 is the electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell according to any one of claims 4 to 6, on each surface of the catalyst layer, and An electrolyte membrane-electrode assembly for a solid alkaline fuel cell, comprising: a diffusion layer disposed in each region of the opening.

  The invention according to claim 8 comprises the electrolyte membrane-electrode assembly for a solid alkaline fuel cell according to claim 7 and a pair of separators, and the electrolyte membrane-electrode for the solid alkaline fuel cell. The joined body is a solid alkaline fuel cell characterized by being sandwiched between the separators.

  According to the present invention, an anion conductive solid polymer electrolyte membrane is used as an electrolyte membrane, and a frame-like gasket for arranging a catalyst layer on the electrolyte membrane is used, thereby reducing the influence of swelling and shrinkage of the electrolyte membrane. In addition, an electrolyte membrane for a solid alkaline fuel cell, an electrolyte membrane for a solid alkaline fuel cell-catalyst layer assembly, and a solid alkaline fuel cell that can form a catalyst layer in a desired shape and have excellent mass productivity An electrolyte membrane-electrode assembly for use and a solid alkaline fuel cell can be provided.

1 is a schematic cross-sectional structure diagram of an electrolyte membrane for a solid alkaline fuel cell according to a first embodiment of the present invention. It is explanatory drawing of the manufacturing method of the electrolyte membrane for solid alkaline fuel cells which concerns on the 1st Embodiment of this invention, Comprising: (a) Process drawing which prepares the gasket 2 in which the contact bonding layer 3 was formed, (b) FIG. 3 is a process diagram for forming the gasket 2 on the anion conductive solid polymer electrolyte membrane 1 with the adhesive layer 3 facing the anion conductive solid polymer electrolyte membrane 1. The typical cross-section figure of the electrolyte membrane-catalyst layer assembly for solid alkaline fuel cells concerning a 3rd embodiment of the present invention. FIG. 6 is a schematic cross-sectional structure diagram in the case where an easy adhesion layer 19 is disposed between an electrolyte membrane 1 and a catalyst layer 5 in an electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell according to a third embodiment of the present invention. The typical cross-section figure of the electrolyte membrane-catalyst layer assembly for solid alkaline fuel cells concerning a 4th embodiment of the present invention. The typical cross-section figure of the electrolyte membrane-catalyst layer assembly for solid alkaline fuel cells concerning a 5th embodiment of the present invention. The typical cross-section figure of the electrolyte membrane-electrode assembly for solid alkaline fuel cells which concerns on the 6th Embodiment of this invention. The typical cross-section figure of the solid alkaline fuel cell which concerns on the 7th Embodiment of this invention.

  Hereinafter, an electrolyte membrane for a solid alkaline fuel cell, an electrolyte membrane for a solid alkaline fuel cell-catalyst layer assembly, an electrolyte membrane for a solid alkaline fuel cell-electrode assembly according to an embodiment of the present invention with reference to the drawings, and A solid alkaline fuel cell will be described. 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.

[First embodiment]
(Electrolyte membrane)
As shown in FIG. 1, an electrolyte membrane 10 for a solid alkaline fuel cell according to a first embodiment of the present invention has an anion conductive solid polymer electrolyte membrane 1 and an alkali-resistant adhesive layer 3 on one surface. And a frame-shaped gasket 2 having an opening 4 for disposing a catalyst layer in the center. The gasket 2 is disposed on one surface of the anion conductive solid polymer electrolyte membrane 1 via an adhesive layer 3.

(Anion conductive solid polymer electrolyte membrane)
The anion conductive solid polymer electrolyte membrane 1 is for conducting hydroxide ions (OH ⁻ ) as anions, and has, for example, a substantially square shape in plan view. It is about 10-300 micrometers, Preferably, it is about 20-200 micrometers. The shape is not limited to a substantially rectangular shape in plan view, and may be a polygonal shape, a substantially circular shape, a substantially elliptical shape, or the like.

  The anion conductive solid polymer electrolyte membrane 1 according to the present embodiment is not particularly limited as long as it is a solid polymer electrolyte membrane that has anion conductivity and does not swell with a solvent component or the like of a catalyst paste composition described later. However, for example, an electrolyte membrane made of a hydrocarbon resin or a fluorine resin can be used.

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

  When using a low concentration alkaline aqueous solution or not using an alkaline aqueous solution, it is preferable to use a hydrocarbon-based electrolyte membrane from the viewpoint of low cost.

  In the alkaline aqueous solution described above, the high concentration can be appropriately changed depending on the type of the alkaline aqueous solution and the like, but in the present embodiment, it means about 2 mol / liter or more, and the low concentration is about 2 mol / liter. Less than about a liter.

  Specific examples of the fluororesin electrolyte membrane include Tosflex (registered trademark) IE-SF34 manufactured by Tosoh Corporation, and fumapem (registered trademark) FAA manufactured by FuMatech. Specific examples of the hydrocarbon-based resin electrolyte membrane include, for example, Aciplex (registered trademark) A201, 2111, 221 manufactured by Asahi Kasei Co., Ltd. and Neocepta (registered trademark) AM-1, AHA manufactured by Tokuyama Corporation. Can be mentioned.

(gasket)
The gasket 2 is for keeping the shape of the catalyst layer and preventing leakage of fuel and oxidant to the outside. The gasket 2 has an opening 4 for disposing a later-described catalyst layer in the center, and has a substantially rectangular frame shape in plan view. The shape is not limited to this, and may be a polygonal frame shape, a substantially circular frame shape, a substantially elliptical frame shape, or the like. The shape of the anion conductive solid polymer electrolyte membrane 1 is preferably matched.

  An adhesive layer 3 having alkali resistance is formed on one surface of the gasket 2. The gasket 2 covers at least the peripheral portion of the surface of the anion conductive solid polymer electrolyte membrane 1 through the adhesive layer 3. The width of the covering peripheral edge is, for example, about 1 to 50 mm, preferably about 2 to 30 mm, and more preferably about 5 to 20 mm. Moreover, it is preferable that the distance from the outer periphery of the anion conductive solid polymer electrolyte membrane 1 to the outer periphery of the gasket 2 is, for example, about 1 to 100 mm. The thickness of the gasket 2 is, for example, about 250 to 3000 μm, preferably about 350 to 2000 μm, and more preferably about 400 to 1500 μm.

  The material of the gasket 2 is not particularly limited as long as it is strong enough to withstand heat and has a liquid and / or gas barrier property that does not leak fuel and oxidant to the outside. For example, a polyethylene terephthalate sheet, a fluorine resin sheet, a silicone rubber sheet, etc. can be exemplified.

(Adhesive layer)
The adhesive layer 3 is for joining the anion conductive solid polymer electrolyte membrane 1 and the gasket 2. The thickness of the adhesive layer 3 is, for example, about 1 to 50 μm, preferably about 3 to 30 μm, and more preferably about 5 to 25 μm.

  The material of the adhesive layer 3 is not particularly limited as long as it has alkali resistance. For example, an adhesive containing acrylic resin, epoxy resin, sulfone resin, vinyl chloride resin, ethylene-vinyl acetate resin, polyamide resin, epoxy acrylate resin, styrene-butadiene rubber resin such as ABS, etc. Or an adhesive containing materials such as styrene, a cyclic skeleton-containing (meth) acrylic acid ester monomer, and a (meth) acrylic acid alkyl ester monomer.

(Method for manufacturing electrolyte membrane)
As shown in FIG. 2, the method for producing an electrolyte membrane for a solid alkaline fuel cell according to the first embodiment of the present invention has an adhesive layer 3 having alkali resistance formed on the surface in advance, and a catalyst layer in the center. The step of preparing the frame-shaped gasket 2 having the opening 4 for forming the anion and the anion conductive solid polymer electrolyte membrane 1, and the gasket in which the adhesive layer 3 faces the anion conductive solid polymer electrolyte membrane 1 side 2 is formed by adhering 2 to the anion conductive solid polymer electrolyte membrane 1.

Below, a manufacturing process is explained in full detail.
(A) First, as shown in FIG. 2 (a), for forming a catalyst layer on one surface, for example, an adhesive layer 3 made of an epoxy-based alkali-resistant resin having a thickness of about 3 to 30 μm is formed. The gasket 2 having the opening 4 is prepared. The gasket 2 is made of, for example, a Teflon (registered trademark) sheet, and has a substantially square frame shape in a plan view, for example, about 10 to 80 mm square and a frame width of about 5 to 50 mm.

(B) Next, in a plan view, for example, an anion conductive solid polymer electrolyte membrane 1 made of, for example, a hydrocarbon resin having about 10 to 80 mm square and a thickness of about 20 to 200 μm is prepared.

(C) Finally, as shown in FIG. 2B, the gasket 2 was positioned on the anion conductive solid polymer electrolyte membrane 1 with the adhesive layer 3 facing the anion conductive solid polymer electrolyte membrane 1 side. Thereafter, adhesion is performed to complete the electrolyte membrane 10 for a solid alkaline fuel cell shown in FIG.

  Such a solid alkaline fuel cell electrolyte membrane 10 has a gasket 2 on which an adhesive layer 3 has been formed in advance on the anion conductive solid polymer electrolyte membrane 1, thus simplifying the manufacturing process. Moreover, since the opening 4 for forming the catalyst layer in the gasket 2 is formed, the process of forming the catalyst layer in the electrolyte membrane 1 is simplified and the shape of the formed catalyst layer is ensured satisfactorily. be able to.

  According to the electrolyte membrane 10 for a solid alkaline fuel cell according to the present embodiment, a catalyst layer having a desired shape can be formed, and the mass productivity is excellent.

[Second Embodiment]
(Electrolyte membrane)
The electrolyte membrane 10A for a solid alkaline fuel cell according to the second embodiment of the present invention is the same as the electrolyte membrane 10 for a solid alkaline fuel cell shown in FIG. The anion conductive solid polymer electrolyte membrane 1 is further disposed on the other surface via the adhesive layer 3. Since other configurations are the same as those of the first embodiment, description thereof is omitted.

  The manufacturing method of the solid alkaline fuel cell electrolyte membrane 10A according to the present embodiment is a first method in which the gasket 2 is further formed on the other surface of the anion conductive solid polymer electrolyte membrane 1 via the adhesive layer 3. This is different from the manufacturing method according to the present embodiment, and the others are the same as those of the first embodiment, and a duplicate description is omitted.

  In the method of manufacturing the electrolyte membrane 10A for the solid alkaline fuel cell according to the present embodiment, the gasket 2 is bonded to the other surface of the anion conductive solid polymer electrolyte membrane 1 in the same manner as in the first embodiment. Thus, the electrolyte membrane 10A for a solid alkaline fuel cell can be manufactured.

  According to the solid alkaline fuel cell electrolyte membrane 10A according to the present embodiment, a catalyst layer having a desired shape can be formed, and the mass productivity is excellent.

[Third embodiment]
(Electrolyte membrane-catalyst layer assembly)
As shown in FIG. 3, the electrolyte membrane-catalyst layer assembly 11 for a solid alkaline fuel cell according to the third embodiment of the present invention has the same solid alkali as in FIG. 1 shown in the first embodiment. The fuel cell electrolyte membrane 10 and a catalyst layer 5 disposed on the surface of the anion conductive solid polymer electrolyte membrane 1 and in the region of the opening 4 are provided. Since other configurations are the same as those of the first embodiment, description thereof is omitted.

(Catalyst layer)
The catalyst layer 5 is composed of a catalyst and an anion electrolyte. The thickness of the catalyst layer 5 may be appropriately set in consideration of the type of electrode substrate, the thickness of the electrolyte membrane, and the like. The thickness is preferably smaller than the thickness of the gasket 2, for example, about 100 to 2500 μm, preferably about 150 to 2000 μm, and more preferably about 200 to 1500 μm.

  When the thickness of the catalyst layer 5 is equal to or greater than the thickness of the gasket 2, when a later-described diffusion layer 15 is provided on the catalyst layer 5, the thickness is increased by that thickness, and further laminated on the later-described layer. A gap is formed between the separator 21 and the current collection efficiency decreases.

(catalyst)
The catalyst comprises catalyst metal fine particles supported on a carrier. Examples of the material for the catalytic metal fine particles include platinum and platinum compounds. Examples of the platinum compound include an alloy of platinum and at least one metal selected from the group consisting of ruthenium, palladium, nickel, molybdenum, iridium, iron and the like. The catalytic metal fine particles not using platinum are at least one selected from the group consisting of iron, cobalt, nickel, palladium, cerium and silver, or an alloy consisting of two or more of these. In the case of an alloy, alloy fine particles containing at least two of iron, cobalt and nickel are preferred. Examples thereof include iron-cobalt-nickel alloys, cobalt-nickel alloys, iron-nickel alloys, and the like, as well as iron-cobalt-nickel alloys. Each ratio of these metals is not limited and can be appropriately selected from a wide range. The particle size of the catalyst metal fine particles is not limited, but is usually about 0.05 to 20 nm, preferably about 0.1 to 10 nm, and most preferably about 0.3 to 5 nm.

  The carrier on which the catalyst metal fine particles are supported is not limited, and a known or commercially available carrier can be used, and examples thereof include alumina particles, silica particles, and carbon particles. From the viewpoint of good corrosion resistance and conductivity, carbon particles, particularly conductive carbon particles are preferred. Examples of the conductive carbon particles include carbon black such as acetylene black, furnace black, channel black, ketjen black, graphite, activated carbon, carbon fiber, carbon nanotube, and carbon nanowire. You may use these 1 type (s) or 2 or more types.

The specific surface area of the carbon particles is not limited, but is usually about 10 to 1500 m ² / g, preferably about 10 to 500 m ² / g. The particle size is not limited, but generally the average primary particle size is about 0.01-1 μm, preferably about 0.01-0.2 μm. The amount of the catalyst metal fine particles supported is appropriately determined depending on the type of the catalyst metal fine particles and the carrier, but is 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. It is.

(Anion electrolyte)
The anion electrolyte is not particularly limited as long as it is an electrolyte that can conduct hydroxide ions (OH ⁻ ) as anions. Specifically, an electrolyte of either a hydrocarbon resin or a fluorine resin can be used.

  Examples of the hydrocarbon resin 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 electrolyte include, for example, a polymer obtained by treating the terminal of a perfluorocarbon polymer having a sulfonic acid group with a diamine to be quaternized, a polymer such as a quaternized product of polychloromethylstyrene, or fumate (registered trademark) manufactured by FuMatech. FAA etc. are mentioned. Among them, the solvent-soluble one is preferable.

  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, (chloromethoxy) methane, 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, morpholine, and the like Monoamines such as heterocyclic amines, and polyamine compounds such as m-phenylenediamine, pyridazine, and pyrimidine can be used.

  The above-mentioned anionic electrolyte is, for example, about 1 to 60% by mass, preferably about 1 to 60% by mass in an organic solvent such as alcohol or ether or a mixed solvent of water and water when preparing a catalyst layer forming paste described later. It is used after being dispersed at a concentration of about 5 to 30% by mass.

  The content (mass ratio) of the catalyst and the anion electrolyte is not limited, but preferably the former: the latter = about 9: 1 to 1: 5, more preferably the former: the latter = 5: 1 to 1: 4.

  The catalyst layer 5 according to the present embodiment may further contain a fluorine resin in addition to the above components. By containing this fluororesin, the binding property of the component is improved, and the catalyst layer 5 becomes stronger and water repellency can be imparted.

  Examples of the fluorine resin 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 properties and water repellency.

  The content in the case of containing a fluororesin is usually about 3 to 25 parts by mass, preferably about 5 to 15 parts by mass with respect to 100 parts by mass of the catalyst.

(Method for producing electrolyte membrane-catalyst layer assembly)
In the method for producing an electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell according to the third embodiment of the present invention, the step of forming the electrolyte membrane for solid alkaline fuel cell 10 and the catalyst layer 5 are formed. A process.

Below, a manufacturing process is explained in full detail.
(A) First, the electrolyte membrane 10 for a solid alkaline fuel cell is formed in the same manner as in the method of the first embodiment.

(B) Next, the catalyst layer 5 is formed as follows.
First, for example, the catalyst and the anion electrolyte are dispersed in a viscosity adjusting solvent (solvent) to prepare a paste composition for forming a catalyst layer. This prepared catalyst paste composition is formed in the gasket 2 opening 4 on the anion conductive solid polymer electrolyte membrane 1 by coating or the like.

  Subsequently, after apply | coating a catalyst paste composition, the catalyst layer 5 is formed by drying. 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.

  Thereby, the electrolyte membrane-catalyst layer assembly 11 for a solid alkaline fuel cell shown in FIG. 3 is completed.

  The solvent for adjusting the viscosity is not 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.

  You may add a fluorine-type resin to the said catalyst paste composition as needed. Examples of the fluorine-based resin include those described above.

  The mixing ratio of the catalyst layer forming paste composition according to the present embodiment is not particularly limited, and may be appropriately selected within a wide range. For example, the anion electrolyte (solid content) may be about 0.2 to 3 parts by mass and the viscosity adjusting solvent may be about 1 to 100 parts by mass with respect to 1 part by mass of the catalyst.

  The method for applying the catalyst paste composition is not particularly limited, and examples thereof include knife coaters, bar coaters, sprays, dip coaters, spin coaters, roll coaters, die coaters, curtain coaters, screen printing, and extrusion coating. General methods can be applied.

  The manufacturing method of the electrolyte membrane-catalyst layer laminate according to the present embodiment is not limited to the method of directly applying and drying the above-described catalyst layer forming paste composition to the anion conductive solid polymer electrolyte membrane 1. For example, after applying and drying the catalyst layer forming paste composition on the transfer substrate, the catalyst layer forming transfer substrate is arranged so that the catalyst layer 5 faces the surface of the anion conductive solid polymer electrolyte membrane 1. Press and crimp. Then, the method of peeling and producing a transfer base material etc. are mentioned.

  The transfer substrate to be applied is not limited. For example, the anion conductive solid polymer electrolyte membrane 1, a gas diffusion substrate such as carbon paper or carbon cloth, or a transfer substrate such as a plastic film can be appropriately selected.

  When a transfer substrate is used, it is provided on at least one of the surface of the anion conductive solid polymer electrolyte membrane 1 to be transferred and the surface of the catalyst layer 5 facing the anion conductive solid polymer electrolyte membrane 1. The easy adhesion layer 19 may be formed. As a result, as shown in FIG. 4, an electrolyte membrane-catalyst layer assembly 11 </ b> A for a solid alkaline fuel cell in which the easy adhesion layer 19 is formed is obtained.

  Further, the easy adhesion layer 19 may be formed in advance on the surface of the anion conductive solid polymer electrolyte membrane 1 on which the catalyst layer 5 is to be formed, even when it is directly applied as described above without using a transfer substrate.

  The easy adhesion layer 19 is for improving the adhesion between the anion conductive solid polymer electrolyte membrane 1 and the catalyst layer 5. The material is not particularly limited as long as the adhesiveness can be maintained and the battery reaction is not impaired. For example, an anionic electrolyte is preferably used.

  When an anion electrolyte is used, the method for coating the electrolyte membrane 1 is not particularly limited. For example, a knife coater, a bar coater, a spray, a dip coater, a spin coater, a roll coater, a die coater, or a curtain coater. General methods such as screen printing can be applied.

  The easy-adhesion layer 19 is formed by applying and drying the anionic electrolyte. A drying temperature is about 40-100 degreeC normally, Preferably it is about 60-80 degreeC. Although depending on the drying temperature, the drying time is usually about 5 minutes to 2 hours, preferably about 30 minutes to 1 hour.

  The thickness of the easy-adhesion layer 19 is not limited as long as the catalyst layer 5 can adhere to the electrolyte membrane 1. Specifically, the thickness of the easy adhesion layer 19 is, for example, about 2 to 20 μm, preferably about 3 to 10 μm.

  A conductive material may be added to the easy adhesion layer 19 in order to increase conductivity. Conductive carbon is preferable as the conductive material. For example, it is manufactured from carbon black such as acetylene black, furnace black, channel black, ketjen black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon nanowire, etc. Things.

  By mixing the conductive material with an anion electrolyte and applying it to the electrolyte membrane 1, the easy adhesion layer 19 imparted with conductivity can be obtained.

  According to the present embodiment, by forming the easy adhesion layer 19, the adhesion between the catalyst layer 5 and the electrolyte membrane 1 is further improved, and MEA (Membrane Electrode Assembly: membrane-electrode catalyst layer assembly) integration is achieved. Long time operation is possible.

  Further, according to the present embodiment, since the catalyst layer 5 is formed in the opening 4 of the gasket 2, a desired shape corresponding to the shape of the opening 4 can be secured, and the catalyst layer 5 is formed by the opening 4. The shape of can be kept good.

  In addition, according to the present embodiment, by using the gasket 2, it is possible to prevent dripping or the like at the end of the catalyst layer 5 even when a low-viscosity catalyst paste is used. Further, since the gasket 2 fixes the peripheral edge of the electrolyte membrane 1, it is possible to suppress deformation of the electrolyte membrane 1 due to swelling of the electrolyte membrane 1 due to the solvent in the catalyst paste and contraction of the electrolyte membrane 1 when the paste is dried.

  According to the electrolyte membrane-catalyst layer assembly 11 for a solid alkaline fuel cell according to the present embodiment, the influence of swelling and shrinkage of the electrolyte membrane can be reduced, and a catalyst layer having a desired shape can be formed. Excellent in mass productivity.

[Fourth embodiment]
(Electrolyte membrane-catalyst layer assembly)
As shown in FIG. 5, the electrolyte membrane-catalyst layer assembly 12 for a solid alkaline fuel cell according to the fourth embodiment of the present invention has an adhesive layer (3 on both sides of the anion conductive solid polymer electrolyte membrane 1. , 7) through which the gasket (2, 6) is disposed, and the same electrolyte membrane 10A for the solid alkaline fuel cell as shown in the second embodiment, and the anion conductive solid polymer electrolyte membrane 1 And catalyst layers (5, 9) disposed on the respective surfaces of the respective openings and in the respective regions of the openings (4, 8). Since other configurations are the same as those of the second and third embodiments, description thereof will be omitted.

  The manufacturing method of the electrolyte membrane-catalyst layer assembly 12 according to the present embodiment is a method in which the gasket 6 and the catalyst layer 9 are further formed on the other surface of the anion conductive solid polymer electrolyte membrane 1 according to the third embodiment. This is different from the manufacturing method in the embodiment, and the others are the same as those in the third embodiment, so that the duplicated explanation is omitted.

  In the method of manufacturing the electrolyte membrane-catalyst layer assembly 12 according to the present embodiment, the gasket 6 is bonded to the other surface of the anion conductive solid polymer electrolyte membrane 1 in the same manner as in the method of the third embodiment. The electrolyte membrane-catalyst layer assembly 12 shown in FIG. 5 can be manufactured by forming through the layer 7 and then forming the catalyst layer 9 in the opening 8.

  According to the electrolyte membrane-catalyst layer assembly 12 for a solid alkaline fuel cell according to the present embodiment, the influence of swelling and shrinkage of the electrolyte membrane can be reduced, and a catalyst layer having a desired shape can be formed. Excellent in mass productivity.

[Fifth embodiment]
(Electrolyte membrane-catalyst layer assembly)
As shown in FIG. 6, the electrolyte membrane-catalyst layer assembly 13 for a solid alkaline fuel cell according to the fifth embodiment of the present invention has the same electrolyte membrane as that shown in FIG. 5 according to the fourth embodiment. -In the catalyst layer assembly 12, the gasket 20 further covers the outer end face of the anion conductive solid polymer electrolyte membrane 1, and the adhesive layer (3, 7) located outside the anion conductive solid polymer electrolyte membrane 1 ) Are adhered to each other. The other configuration is the same as that of the fourth embodiment, and a description thereof will be omitted.

  In the manufacturing method of the electrolyte membrane-catalyst layer assembly 13 according to the present embodiment, the outer end face of the anion conductive solid polymer electrolyte membrane 1 is covered with the gasket 20 and the adhesive layers (3, 7) located on the outside are covered with each other. The method of bonding and forming is different from the manufacturing method in the fourth embodiment, and the others are the same as those in the fourth embodiment, and thus the duplicated explanation is omitted.

  In the manufacturing method of the electrolyte membrane-catalyst layer assembly 13 according to the present embodiment, the electrolyte membrane-catalyst layer assembly 12 shown in FIG. 5 is formed and then adhered to the surface in the same manner as in the fourth embodiment. Using the gasket (2, 6) larger than the anion conductive solid polymer electrolyte membrane 1 formed with the layers (3, 7), the gasket (2, 2) located outside the anion conductive solid polymer electrolyte membrane 1 is used. 6) It forms on both surfaces of the anion conductive solid polymer electrolyte membrane 1 so that the peripheral parts may adhere | attach. Thereby, the electrolyte membrane-catalyst layer assembly 13 shown in FIG. 6 can be manufactured.

  According to the present embodiment, the gasket (2, 6) covers the outer end faces of the anion conductive solid polymer electrolyte membrane 1 and the adhesive layers (3, 7). Leakage can be suppressed.

  According to the electrolyte membrane-catalyst layer assembly 13 for a solid alkaline fuel cell according to the present embodiment, the influence of swelling and shrinkage of the electrolyte membrane can be reduced, and a catalyst layer having a desired shape can be formed. Excellent in mass productivity.

[Sixth embodiment]
(Electrolyte membrane-electrode assembly)
As shown in FIG. 7, an electrolyte membrane for a solid alkaline fuel cell-electrode assembly 14 according to a sixth embodiment of the present invention is the same electrolyte membrane as in FIG. 5 shown in the fourth embodiment. The catalyst layer assembly 12 and diffusion layers (15, 16) disposed on the respective surfaces of the catalyst layers (5, 9) and in the respective regions of the openings (4, 8) are provided. The other configuration is the same as that of the fourth embodiment, and a description thereof will be omitted. Needless to say, the electrolyte membrane-catalyst layer assembly 12 may be the same electrolyte membrane-catalyst layer assembly 13 as shown in FIG. 6 in the fifth embodiment.

(Diffusion layer)
The diffusion layer (15, 16) diffuses and distributes a liquid or gas that becomes a fuel or an oxidant to the catalyst layer (5, 9) and has a current collecting function. The thickness of the layer is not limited, and is, for example, about 150 to 800 μm, preferably about 200 to 600 μm.

  The material of the diffusion layer (15, 16) is not particularly limited as long as it can transmit liquid or gas. Preferably, it is made of a porous conductive material. For example, in addition to metals such as iron, cobalt, nickel, palladium, silver, ruthenium, iridium, molybdenum, and manganese, carbon can be widely selected.

  In the case of a diffusion layer that allows liquid to permeate, it should be porous, and its porosity is, for example, about 10 to 80%, preferably about 30 to 70%. When the diffusion layer is made of a metal, nickel or silver is particularly preferable from the viewpoint of excellent catalytic activity.

  When the diffusion layer that allows gas to pass through is made of carbon, conductive carbon is preferable from the viewpoint of gas diffusibility and conductivity. For example, in addition to carbon black such as acetylene black, furnace black, channel black and ketjen black, those manufactured from graphite, activated carbon, carbon fiber, carbon nanotube, carbon nanowire and the like can be mentioned.

  As the diffusion layers (15, 16), diffusion layers of various liquids and gases constituting a fuel electrode and an air electrode, which are generally used for fuel cells, can be used.

(electrode)
In the present embodiment, the electrodes (17, 18) are composed of catalyst layers (5, 9) and diffusion layers (15, 16). The electrodes (17, 18) are preferably formed with the same thickness as that including the gasket (2, 6) and the adhesive layer (3, 7) from the viewpoint of current collection efficiency. Therefore, the catalyst layers (5, 9) formed on the anion conductive solid polymer electrolyte membrane 1 are preferably formed smaller than the thickness of the gasket (2, 6).

  When the catalyst layers (5, 9) are formed to be equal to or thicker than the gasket (2, 6), the electrodes (15, 16) having the diffusion layers (15, 16) formed on the catalyst layers (5, 9) 17, 18) is thicker than the gasket (2, 6). If the thickness of the electrode (17, 18) is larger than the thickness of the gasket (2, 6), a step is generated between the later-described separator disposed on the electrode (17, 18) and the gasket (17, 18). End up. If a level difference occurs, fuel and oxidant leak to the outside, leading to a decrease in current collection efficiency.

  The manufacturing method of the electrolyte membrane-electrode assembly 14 according to the present embodiment is different from the manufacturing method according to the fourth embodiment in the method of forming the diffusion layers (15, 16). Since it is the same as that of embodiment, the overlapping description is abbreviate | omitted.

  In the manufacturing method of the electrolyte membrane-electrode assembly 14 according to the present embodiment, after the electrolyte membrane-catalyst layer assembly 12 shown in FIG. 5 is formed in the same manner as in the fourth embodiment, the diffusion layer (15 16), the electrolyte membrane-electrode assembly 14 shown in FIG. 7 can be manufactured.

  According to the present embodiment, by providing the diffusion layers (15, 16), the fuel and gas are supplied to the porous liquid and gas diffusion layers (15, 16), thereby diffusing the fuel and gas. Excellent fuel usage rate. Further, since the liquid and gas diffusion layers are made of a porous conductive material, the current collection effect is improved.

  According to the electrolyte membrane-electrode assembly 14 for a solid alkaline fuel cell according to the present embodiment, the influence of swelling and shrinkage of the electrolyte membrane can be reduced, and a catalyst layer having a desired shape can be formed. Excellent mass productivity.

[Seventh embodiment]
(Fuel cell)
As shown in FIG. 8, the solid alkaline fuel cell 25 according to the seventh embodiment of the present invention includes an electrolyte membrane-electrode assembly 14 similar to that shown in FIG. Separators (21, 22). The electrolyte membrane-electrode assembly 14 is sandwiched between the separators (21, 22). The other configuration is the same as that of the sixth embodiment, and a description thereof will be omitted.

(Separator)
The separator 21 is for supplying an oxidant gas to the cathode electrode 17 and has an oxidant gas flow path 23 for circulating the oxidant gas. On the other hand, the separator 22 is for supplying fuel to the anode electrode 18 and has a fuel flow path 24 for circulating the fuel.

  The separator (21, 22) may be made of any material that has stable conductivity even in the environment within the fuel cell 25. In general, a carbon plate having a flow path is used. The separators (21, 22) are made of a metal such as stainless steel, and a coating made of a conductive material such as chromium, a platinum group metal or oxide thereof, or a conductive polymer is formed on the surface of the metal. There may be. Similarly, it is possible to use a metal made of a metal and plated on the surface of the metal with a material such as silver, a platinum group composite oxide, or chromium nitride.

  The separators (21, 22) can have a function as a current collector when used in a fuel cell in which a plurality of fuel cells 25 are stacked.

(fuel)
Examples of the fuel include monohydric alcohols such as methanol, ethanol, and propanol, and alcohols such as polyhydric alcohols such as ethylene glycol and propylene glycol. An aqueous alkaline solution is preferably used as the aqueous fuel solution. Examples of the alkaline aqueous solution include KOH solution and NaOH solution. A fuel aqueous solution is prepared by mixing these alkali sources and fuel.

  The manufacturing method of the solid alkaline fuel cell 25 according to the present embodiment is different from the manufacturing method according to the sixth embodiment in the method of forming the separators (21, 22) on the electrolyte membrane-electrode assembly 14. Since the others are the same as those of the sixth embodiment, a duplicate description is omitted.

  In the method of manufacturing the solid alkaline fuel cell 25 according to the present embodiment, the separator 21 in which the oxidant gas flow path 23 is formed is disposed so that the oxidant gas flow path 23 is in contact with the cathode electrode 17 side, and the fuel flow The solid alkaline fuel cell 25 shown in FIG. 8 can be manufactured by disposing the separator 22 in which the passage 24 is formed so that the fuel passage 24 is in contact with the anode electrode 18 side.

(Operating principle)
The solid alkaline fuel cell 25 according to the present embodiment can generate power as described below.

First, oxygen (O ₂ ) is supplied to the cathode electrode 17 side through the oxidant gas flow path 23, and becomes fuel to the anode electrode 18 side through the fuel flow path 24, for example, ethanol (C ₂ H ₅ OH) is mixed with an aqueous KOH solution. In the cathode electrode 17, water (H ₂ O) that has reached through the anion conductive solid polymer electrolyte membrane 1 and electrons (e ⁻ ) that have reached through an external circuit (not shown) are converted into the cathode electrode 17. The catalyst of the catalyst layer 5 reacts with the supplied oxygen to generate hydroxide ions (OH ⁻ ), and the reduction reaction of the formula (1) proceeds.
Cathode electrode: O ₂ + 2H ₂ O + 4e ⁻ → 4OH ⁻ (1)

The generated hydroxide ions move from the cathode electrode 17 side to the anode electrode 18 side through the anion conductive solid polymer electrolyte membrane 1. On the anode electrode 18 side, hydroxide ions that have passed through the anion conductive solid polymer electrolyte membrane 1 react with ethanol as fuel to generate electrons, and the oxidation reaction of formula (2) proceeds. .
Anode electrode: (1/3) C ₂ H ₅ OH + 4OH ⁻ → (2/3) CO ₂ + 3H ₂ O + 4e ⁻ (2)

The generated electrons move from the anode electrode 18 side to the cathode electrode 17 side via an external circuit (not shown) and are supplied to the cathode electrode 17. As a whole, the battery reaction of Formula (3) in which ethanol is oxidized by oxygen to generate carbon dioxide and water proceeds to generate power.
Battery reaction: (1/3) C ₂ H ₅ OH + O ₂ → (2/3) CO ₂ + H ₂ O ... (3)

  Carbon dioxide generated on the anode electrode 18 side is discharged to the outside together with the remaining ethanol aqueous solution. Further, the water generated on the cathode electrode 17 side is discharged to the outside as water vapor together with the remaining oxygen.

  The solid alkaline fuel cell 25 according to the present embodiment is provided with an anion conductive solid polymer electrolyte membrane 1. Therefore, it is possible to obtain a solid alkaline fuel cell 25 having high power generation efficiency by suppressing high electrolyte membrane strength and permeation of organic fuel (for example, ethanol crossover).

  According to the solid alkaline fuel cell 25 according to the present embodiment, the influence of swelling and shrinkage of the electrolyte membrane can be reduced, a catalyst layer having a desired shape can be formed, and the mass productivity is excellent.

[Other embodiments]
The present invention has been described in detail with the first to seventh embodiments described above. However, for those skilled in the art, the present invention is limited to the first to seventh embodiments described in this specification. Obviously it is not. The present invention can be implemented as modifications and changes without departing from the spirit and scope of the present invention defined by the description of the scope of claims. Therefore, the description of the present specification is for illustrative purposes and does not have any limiting meaning to the present invention.

  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]
(Catalyst layer forming paste)
First, a chloromethyl compound of a copolymer of aromatic polyether sulfonic acid and aromatic polythioether sulfonic acid was aminated to obtain 100 g of a 5% by mass anion (hydroxide ion) electrolyte.

  Next, 2 g of silver catalyst-supported carbon (silver supported amount: 40% by mass, manufactured by E-TEK), 10 g of isopropyl alcohol, 10 g of ethanol, 0.2 g of 60% by mass of polytetrafluoroethylene dispersion (manufactured by Aldrich), the above A paste composition for forming a catalyst layer on the cathode electrode 17 side was prepared by adding 20 g of the 5% by mass anionic electrolyte obtained in the above and 6 g of water and stirring and mixing them with a disperser.

  Further, 2 g of nickel catalyst-supported carbon (Ni supported amount: 40% by mass), 10 g of isopropyl alcohol, 10 g of ethanol, 0.2 g of 60% by mass of polytetrafluoroethylene dispersion (manufactured by Aldrich), 5 mass obtained above. A paste composition for forming a catalyst layer on the anode electrode 18 side was prepared by adding 20 g of% anionic electrolyte and 6 g of water and stirring and mixing them with a disperser.

(Electrolyte membrane-electrode assembly)
As the anion conductive solid polymer electrolyte membrane 1, Aciplex A-221 (thickness 130 to 190 μm: manufactured by Asahi Kasei Co., Ltd.) and cut into a size of 60 × 60 mm were used.

  Next, the electrolyte membrane 10 for solid alkaline fuel cells was produced as follows. A gasket in which an adhesive layer 3 made of an epoxy resin adhesive (Eflex manufactured by Konishi Co., Ltd.) was formed on one surface of a gasket 2 made of a Teflon (registered trademark) sheet having an opening 4 of 50 × 50 mm was used. This gasket was formed by positioning and adhering to one side of a 60 × 60 mm anion conductive solid polymer electrolyte membrane 1 such that the adhesive layer 3 faces the electrolyte membrane 1 side.

Next, the catalyst layer-forming paste composition on the cathode electrode 17 side is passed through the gasket opening 4 of the anion conductive solid polymer electrolyte membrane 1 so that the dried silver mass of the catalyst layer 5 is 4 mg / cm ^2. To prepare an electrolyte membrane-catalyst layer assembly 11. The thickness of the catalyst layer 5 was 300 μm.

  Next, on the other surface of the electrolyte membrane 1 of the obtained electrolyte membrane-catalyst layer assembly 11, on one side of the gasket 2 made of a Teflon (registered trademark) sheet having an opening 8 of 50 × 50 mm similar to the above. A gasket on which an adhesive layer 7 made of an epoxy resin adhesive (Eflex manufactured by Konishi Co., Ltd.) was formed was positioned and adhered so that the adhesive layer 7 faced the electrolyte membrane 1 side.

Next, the catalyst layer forming paste composition on the anode electrode 18 side is applied through the gasket opening 8 so that the nickel mass after drying of the catalyst layer 9 is 4 mg / cm ^2, and the electrolyte membrane-catalyst layer bonding is performed. A body 12 was produced. The thickness of the catalyst layer 9 was 300 μm.

  Next, a diffusion layer 15 composed of a 49 × 49 mm gas diffusion layer (carbon cloth LT-1200W: manufactured by E-TEK) is formed on the catalyst layer 5 exposed from the gasket opening 4 on the cathode electrode 17 side. did. Next, a diffusion layer 16 composed of a 49 × 49 mm liquid diffusion layer (foamed nickel: manufactured by Mitsubishi Materials Corporation) is formed on the catalyst layer 9 exposed from the gasket opening 8 on the anode electrode 18 side. 1 electrolyte membrane-electrode assembly 14 was produced.

[Example 2]
In the same manner as in Example 1, except that an acrylic resin adhesive (instant adhesive 7005S manufactured by Sumitomo 3M Limited) was used instead of the epoxy resin adhesive for the adhesive layer (3, 7), an electrolyte membrane- An electrode assembly 14 was produced.

[Example 3]
In the same manner as in Example 1, except that a vinyl chloride resin adhesive (Scotch 6252N manufactured by Sumitomo 3M Limited) was used in place of the epoxy resin adhesive for the adhesive layers (3, 7), an electrolyte membrane-electrode A joined body 14 was produced.

[Example 4]
In the same manner as in Example 1, except that an ethylene-vinyl acetate resin adhesive (Scotch Weld 3738 manufactured by Sumitomo 3M) was used instead of the epoxy resin adhesive for the adhesive layers (3, 7), the electrolyte A membrane-electrode assembly 14 was produced.

[Example 5]
An electrolyte membrane-electrode assembly 14 was produced in the same manner as in Example 1 except that the easy adhesion layer 19 was formed between the electrolyte membrane 1 and the catalyst layers (5, 9). The easy adhesion layer 19 was applied by spraying the 5% by mass anion electrolyte solution obtained in Example 1 through the openings (4, 8) of the gaskets (2, 6) bonded to both sides of the electrolyte membrane 1. And formed by drying at 50 ° C. for 10 minutes. As a result, an anion conductive solid polymer electrolyte membrane 1 with a gasket on which the easy adhesion layer 19 was formed was produced.

[Example 6]
The cathode-side and anode-side paste compositions prepared in the same manner as in Example 1 were used as a metal amount on a transfer substrate (PET film: E3120, manufactured by Toyobo Co., Ltd .: thickness 12 μm), silver on the cathode side, and anode the on the side nickel, after the weight after drying was coated so that each becomes ^{4mg / cm 2, 20mg / cm} 2, followed by drying for 15 minutes at 100 ° C., which is formed of a catalyst layer 5,9 anode Side and cathode side transfer films were prepared.

  Next, the 5 mass% anion obtained in Example 1 was passed through the openings (4, 8) of the gasket (2, 6) bonded to both sides of the electrolyte membrane with gasket 1 produced in the same manner as in Example 1. The electrolyte solution was applied by spraying and dried at 50 ° C. for 10 minutes to form the easy adhesion layer 19.

  Next, after placing the anode-side and cathode-side transfer films (50 × 50 mm) prepared above on the easy-adhesion layers 19 formed on both surfaces of the electrolyte membrane 1, heat was applied at a pressure of 5 MPa and a temperature of 60 ° C. for 5 minutes. Crimped. Subsequently, the transfer base material was peeled off to produce an electrolyte membrane-catalyst layer laminate in which an easy adhesion layer 19 was formed between the electrolyte membrane 1 and the catalyst layers (5, 9).

Next, on the catalyst layer 5 exposed from the gasket opening 4 on the cathode electrode 17 side, 49
A diffusion layer 15 made of a gas diffusion layer of × 49 mm (carbon cloth LT-1200W: manufactured by E-TEK) was formed. Next, a diffusion layer 16 composed of a 49 × 49 mm liquid diffusion layer (foamed nickel: manufactured by Mitsubishi Materials Corporation) is formed on the catalyst layer 9 exposed from the gasket opening 8 on the anode electrode 18 side. 6 electrolyte membrane-electrode assembly 14 was produced.

[Example 7]
The cathode electrode 17 was prepared using carbon paper (35BC, manufactured by SGL, thickness: 320 μm) instead of the carbon cloth in the gas diffusion layer in Example 1, and the anode electrode 18 was formed in the same manner as in Example 1. Produced. Next, an anion conductive solid polymer electrolyte membrane 1 with a gasket on which an easy adhesion layer 19 was formed was produced in the same manner as in Example 5.

  Next, the anode electrode (50 × 50 mm) and the cathode electrode (50 × 50 mm) prepared above are arranged on both surfaces of the produced anion conductive solid polymer electrolyte membrane 1, and then 5 ° C. at a pressure of 5 MPa and a temperature of 60 ° C. The electrolyte membrane-electrode assembly 14 of Example 7 in which the easy-adhesion layer 19 was formed between the electrolyte membrane 1 and the catalyst layers (5, 9) was manufactured by thermocompression bonding for minutes.

[Example 8]
In the formation of the easy-adhesion layer 14 of Example 6, an anion electrolyte solution obtained by mixing 1 g of vapor grown carbon fiber (VGCF; Showa Denko KK) with 5 g of the 5 mass% anion electrolyte solution obtained in Example 1 was used. An electrolyte membrane-electrode assembly 14 of Example 8 was produced in the same manner as in Example 6 except that the easy-adhesion layer 19 was formed using the same.

[Comparative Example 1]
An electrolyte membrane-electrode assembly 14 was prepared in the same manner as in Example 1 except that a silicone resin sheet was used instead of the Teflon (registered trademark) sheet and a gasket that did not form the adhesive layer (3, 7) was used. Produced. The silicone resin sheet was bonded to the anion conductive solid polymer electrolyte membrane 1 using self-adhesiveness.

[Comparative Example 2]
In the same manner as in Example 1, except that a urea resin adhesive (SC manufactured by Toyo Plywood Co., Ltd.) was used instead of the epoxy resin adhesive for the adhesive layer (3, 7), an electrolyte membrane-electrode assembly 14 was produced.

[Comparative Example 3]
An electrolyte membrane-electrode assembly was obtained in the same manner as in Example 1 except that a phenolic resin adhesive (Cemedine 575, manufactured by Cemedine) was used for the adhesive layers (3, 7) instead of the epoxy resin adhesive. 14 was produced.

[Comparative Example 4]
In the same manner as in Example 1, except that a polyurethane resin adhesive (Cemedine UM700 manufactured by Cemedine Co., Ltd.) was used instead of the epoxy resin adhesive for the adhesive layers (3, 7), an electrolyte membrane-electrode assembly. 14 was produced.

(Performance evaluation)
Separators (21, 22) are arranged on both main surfaces of the electrolyte membrane-electrode assemblies 14 obtained in Examples 1 to 8 and Comparative Examples 1 to 4, respectively, and a solid alkaline fuel cell as shown in FIG. 25 was produced and the battery performance was evaluated.

  The performance evaluation was performed as follows. That is, the operating temperature of the fuel cell 25 is set to about 60 ° C., oxygen gas is supplied to the oxidant gas flow path 23 of the cathode electrode 17 side separator 21, and ethanol aqueous solution is supplied to the fuel flow path 24 of the anode electrode 18 side separator 22. Then, the open electromotive force (OCV) was examined. The results are shown in Table 1.

  As shown in Table 1, Examples 1 to 8 all exhibited higher open electromotive force than Comparative Examples 1 to 4.

DESCRIPTION OF SYMBOLS 1 ... Anion conductive solid polymer electrolyte membrane 2, 6, 20 ... Gasket 3, 7 ... Adhesive layer 4, 8 ... Opening 5,9 ... Catalyst layer 10 ... Solid Electrolyte membrane for alkaline fuel cell 11, 11A, 12, 13 ... Solid alkaline fuel cell electrolyte membrane-catalyst layer assembly 14 ... Solid alkaline fuel cell electrolyte membrane-electrode assembly 15, 16, ..Diffusion layer 17 ... Electrode (cathode electrode)
18 ... Electrode (Anode electrode)
DESCRIPTION OF SYMBOLS 19 ... Easy-adhesion layer 21, 22 ... Separator 23 ... Oxidant gas flow path 24 ... Fuel flow path 25 ... Solid alkaline fuel cell

Claims (8)

An anion conductive solid polymer electrolyte membrane;
A frame-shaped gasket having an alkali-resistant adhesive layer on one side and an opening for disposing a catalyst layer in the center;
An electrolyte membrane for a solid alkaline fuel cell, wherein the gasket is disposed on one surface of the anion conductive solid polymer electrolyte membrane via the adhesive layer.   2. The electrolyte membrane for a solid alkaline fuel cell according to claim 1, wherein the gasket is further disposed on the other surface of the anion conductive solid polymer electrolyte membrane via the adhesive layer. An electrolyte membrane for a solid alkaline fuel cell according to claim 1,
A catalyst layer disposed on the surface of the anion conductive solid polymer electrolyte membrane and in the region of the opening;
An electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell, comprising: The electrolyte membrane for a solid alkaline fuel cell according to claim 2,
A catalyst layer disposed on each surface of the anion conductive solid polymer electrolyte membrane and in each region of the opening;
An electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell, comprising:   The electrolyte membrane-catalyst layer assembly according to claim 3 or 4, wherein the catalyst layer has a thickness smaller than that of the gasket.   The gasket further covers an outer end face of the anion conductive solid polymer electrolyte membrane, and the adhesive layers located outside the anion conductive solid polymer electrolyte membrane are bonded to each other. The electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell according to claim 4 or 5. The electrolyte membrane-catalyst layer assembly for a solid alkaline fuel cell according to any one of claims 4 to 6,
A diffusion layer disposed on each surface of the catalyst layer and in each region of the opening;
An electrolyte membrane-electrode assembly for a solid alkaline fuel cell, comprising: An electrolyte membrane-electrode assembly for a solid alkaline fuel cell according to claim 7,
A pair of separators;
A solid alkaline fuel cell, wherein the electrolyte membrane-electrode assembly for a solid alkaline fuel cell is sandwiched between the separators.

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