JP5581618B2 - Solid polymer fuel cell member, catalyst layer with an edge seal-electrolyte membrane laminate, electrode with edge seal-electrolyte membrane laminate, and method for producing a polymer electrolyte fuel cell - Google Patents

Description

  The present invention relates to a transfer sheet, a polymer electrolyte fuel cell member, and a method for producing a polymer electrolyte fuel cell member and an electrode-electrolyte membrane laminate with an edge seal.

  The polymer electrolyte fuel cell has a low operating temperature and low resistance of the electrolyte membrane, and uses a highly active catalyst, so it can obtain high output even with a small size. Is expected. This polymer electrolyte fuel cell has a configuration in which a gasket is attached to an electrode-electrolyte membrane laminate in which electrodes are formed on both sides of the electrolyte membrane, and this is sandwiched by separators from both sides. For the purpose of preventing this, a device with an edge seal attached has been proposed.

  As a method of attaching this edge seal, for example, FIG. 4 of Patent Document 1 shows a long structure having openings on both surfaces of a catalyst layer-electrolyte membrane laminate in which a plurality of catalyst layers are formed on a long electrolyte membrane. A method of adhering a scale edge seal is disclosed.

JP 2007-180031 A

  However, in the above-described method, since the catalyst layer is larger than the opening of the edge seal, when the catalyst layer-electrolyte membrane laminate and the edge seal are overlapped, the edge peripheral region of the opening of the edge seal and the catalyst There is a portion where the outer peripheral edge of the layer overlaps. In this overlapping portion, stress is concentrated when the catalyst layer-electrolyte membrane laminate and the edge seal are pressed with a drum, and the electrolyte membrane corresponding to this portion becomes thinner than the other portions. There is. Then, this invention makes it a subject to provide the method which can reduce that electrolyte membrane becomes thin locally.

  The first transfer sheet according to the present invention comprises a base material, an edge seal formed on the base material, having an opening, and a catalyst layer formed on the base material in the opening. I have.

  This transfer sheet is superposed on the electrolyte membrane and applied with pressure to transfer the catalyst layer and the edge seal to the electrolyte membrane to produce a catalyst layer-electrolyte membrane laminate with an edge seal. In this transfer, since the catalyst layer and the edge seal do not overlap each other, it is possible to prevent the electrolyte membrane from being locally thinned by applying a uniform pressure to the electrolyte membrane. And when the thickness of the electrolyte membrane is uniform in this way, it leads to long-term stabilization of battery performance.

  The second transfer sheet according to the present invention is a long base material, an edge seal formed on the base material, and having a plurality of openings arranged in the length direction of the base material; And a catalyst layer formed on the substrate.

  Similarly, since this transfer sheet does not overlap the catalyst layer and the edge seal, the same effect as described above can be obtained. Moreover, since this transfer sheet is long, productivity when producing a catalyst layer-electrolyte membrane laminate with an edge seal from this transfer sheet can be improved.

  The first member for a polymer electrolyte fuel cell according to the present invention comprises an electrolyte membrane, and any one of the above transfer sheets bonded to at least one surface of the electrolyte membrane, and the transfer sheet includes: The catalyst layer and the edge seal are adhered to the electrolyte membrane. According to this, since any one of the above transfer sheets is provided, it is possible to prevent the electrolyte membrane from being locally thinned. As a result, it is possible to reduce the solid height using the solid polymer fuel cell member. Long-term stabilization of the cell performance of the molecular fuel cell can be achieved.

  The second polymer electrolyte fuel cell member according to the present invention includes an electrolyte membrane and any one of the transfer sheets bonded to both surfaces of the electrolyte membrane, and each of the transfer sheets includes the A catalyst layer and an edge seal are adhered to the electrolyte membrane, and the sizes of the catalyst layers of the respective transfer sheets are different from each other. Since this solid polymer fuel cell member includes any one of the above transfer sheets, the electrolyte membrane can be prevented from becoming locally thin. In addition, since the sizes of the catalyst layers are different from each other, for example, even when positional deviation occurs due to the size of the anode catalyst layer being larger than that of the cathode catalyst layer, the cathode catalyst layer is in the thickness direction. Since the region without the anode catalyst layer can be eliminated through the cathode, carbon corrosion of the cathode catalyst layer can be prevented.

  The first method for producing a polymer electrolyte fuel cell member according to the present invention includes an electrolyte membrane supplying step for supplying an electrolyte membrane, and a transfer sheet in which an edge seal having an opening is bonded to a substrate. A transfer sheet supplying step for supplying the transfer sheet having a catalyst layer formed on the substrate in the opening, and the transfer sheet is placed so that the edge seal and the catalyst layer face the electrolyte membrane. And a pressing step that is disposed on at least one surface of the electrolyte membrane and applies pressure so that the edge seal of the transfer sheet and the catalyst layer adhere to the electrolyte membrane.

  According to this method for producing a polymer electrolyte fuel cell member, since the edge seal and the catalyst layer formed on the base material do not overlap each other, the transfer sheet and the electrolyte membrane are overlapped and pressure is applied. However, it is possible to apply a uniform pressure to the electrolyte membrane, and consequently to prevent the electrolyte membrane from becoming thin locally.

  Further, the second method for producing a polymer electrolyte fuel cell member according to the present invention includes an electrolyte membrane supplying step for supplying a long electrolyte membrane, and a long length formed with a plurality of openings aligned in the longitudinal direction. And a transfer sheet supplying step of supplying the transfer sheet in which a catalyst layer is formed on the base material in each opening, and the edge seal The transfer sheet is disposed on at least one surface of the electrolyte membrane so that the seal and each catalyst layer face the electrolyte membrane, and pressure is applied so that the edge seal and the catalyst layer of the transfer sheet adhere to the electrolyte membrane. And a pressing process.

  Similarly to the above-described manufacturing method, the method for producing the solid polymer fuel cell member can apply pressure evenly to the electrolyte membrane even when the transfer sheet and the electrolyte membrane are overlaid. Can be prevented from becoming locally thin.

  In this second method for producing a polymer electrolyte fuel cell member, the electrolyte membrane is conveyed in the longitudinal direction in the electrolyte membrane supply step, the transfer sheet is conveyed in the same direction as the electrolyte membrane in the transfer sheet supply step, and the pressing step It is preferable that the transfer sheet is adhered to the electrolyte membrane by sandwiching the electrolyte membrane being transferred and the transfer sheet between a pair of rollers.

  Moreover, the process of further cutting | disconnecting the elongate electrolyte membrane to which the transfer sheet was adhere | attached between each opening part may be included.

  The method for producing an electrode-electrolyte membrane laminate with an edge seal according to the present invention includes any one of the above-described methods for producing a polymer electrolyte fuel cell member, a step of peeling the base material of the transfer substrate, and the catalyst. Laminating a conductive porous substrate on the layer. In this method, since any one of the above-described methods for producing a polymer electrolyte fuel cell member is employed, it is possible to prevent the electrolyte membrane from being locally thinned.

  Further, a method for producing a polymer electrolyte fuel cell according to the present invention includes a method for producing the electrode-electrolyte membrane laminate with an edge seal, a step of installing a gasket on the edge seal, and the gasket is installed. Sandwiching the electrode-electrolyte membrane laminate with edge seal from both sides with a separator. Since this method includes the manufacturing method of the electrode-electrolyte membrane laminate with the edge seal, it is possible to prevent the electrolyte membrane from being locally thinned.

  The apparatus for producing a polymer electrolyte fuel cell member according to the present invention includes an electrolyte membrane supply unit that supplies a long electrolyte membrane and a long edge seal formed with a plurality of openings arranged in the longitudinal direction. Is a transfer sheet adhered on a long base material, and a transfer sheet supply section for supplying the transfer sheet having a catalyst layer formed on the base material in each opening, the edge seal, and each A pressurizing unit that applies pressure across the electrolyte membrane and the transfer sheet in a state where the transfer sheet is disposed on at least one surface of the electrolyte membrane so that the catalyst layer faces the electrolyte membrane. Yes.

  According to this manufacturing apparatus, since the edge seal and the catalyst layer formed on the base material do not overlap each other, even if this transfer sheet and the electrolyte membrane are overlapped and pressure is applied at the pressurizing portion, the electrolyte membrane is applied. On the other hand, it is possible to apply pressure uniformly, and as a result, it is possible to prevent the electrolyte membrane from being locally thinned.

  According to the present invention, it is possible to prevent the electrolyte membrane from being locally thinned, and thus to stabilize the battery performance of the polymer electrolyte fuel cell for a long period of time.

FIG. 1 is a schematic side view showing an apparatus for producing a polymer electrolyte fuel cell member according to this embodiment. FIG. 2 is a plan view showing a transfer sheet according to the present embodiment. 3 is a cross-sectional view taken along line AA in FIG. FIG. 4 is a side cross-sectional view of the polymer electrolyte fuel cell member according to this embodiment. FIG. 5 is an explanatory view showing a method for producing a polymer electrolyte fuel cell from a long polymer electrolyte fuel cell member according to this embodiment. FIG. 6 is an explanatory view showing a transfer sheet manufacturing method according to another embodiment. FIG. 7 is a plan view showing a transfer sheet according to another embodiment.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of an apparatus for producing a polymer electrolyte fuel cell member according to the present invention will be described with reference to the drawings. In the following description, the right side of FIG. 1 is referred to as downstream and the left side is referred to as upstream. Moreover, the arrow Y in each figure has shown the advancing direction of an electrolyte membrane, a transfer sheet, a member for a polymer electrolyte fuel cell, etc.

  As shown in FIG. 1, the solid polymer fuel cell member manufacturing apparatus 1 includes an electrolyte membrane supply unit 2 that supplies a long electrolyte membrane 6 and a transfer sheet supply unit that supplies a long transfer sheet 7. 3, a pressure unit 4 for temporarily attaching the electrolyte membrane 6 and the transfer sheet 7, and a winding for winding up the polymer electrolyte fuel cell member 8 having the transfer sheet 7 temporarily attached to the electrolyte membrane 6 in a roll shape Part 5.

  The electrolyte membrane supply unit 2 includes a first rotating shaft 21 in which the electrolyte membrane 6 wound in a roll shape is set, and a first drive mechanism (not shown) that rotates the first rotating shaft 21. The first drive mechanism is configured to send the electrolyte membrane 6 set on the first rotation shaft downstream by rotating the first rotation shaft 21. Although the conveyance speed of this electrolyte membrane 6 is not specifically limited, It is preferable to set it as 0.1-5 m / min.

The transfer sheet supply unit 3 includes a second rotating shaft 31 on which the transfer sheet 7 wound in a roll shape is set, and a second drive mechanism (not shown) that rotates the second rotating shaft 31. The second drive mechanism is configured to send the transfer sheet 7 set on the second rotation shaft 31 downstream by rotating the second rotation shaft 31. The transfer speed of the transfer sheet 7 is not particularly limited, but is preferably substantially the same as the transfer speed of the electrolyte membrane 6. As shown in FIGS. 2 and 3, the transfer sheet 7 wound in a roll shape has a long base 71, and an edge seal 72 is bonded to the base 71. The edge seal 72 has a plurality of openings arranged in the longitudinal direction at intervals d ₁ , and a catalyst layer 73 is formed on the base material 71 in each opening.

  As described above, the pressure unit 4 includes a pair of pressure rollers 41 installed so as to sandwich the electrolyte film 6 and the transfer sheet 7 fed from the electrolyte film supply unit 2 and the transfer sheet supply unit 3 from above and below. It is configured. The electrolyte membrane 6 and the transfer sheet 7 are pressed by the pressure roller 41, and the transfer sheet 7 is temporarily attached to the electrolyte membrane 6, thereby producing the polymer electrolyte fuel cell member 8. In addition, the pressure roller 41 may heat the electrolyte membrane 6 and the transfer sheet 7 by, for example, a heating medium flowing therein, and the temperature of the pressure roller 41 at this time is preferably 200 degrees or less. More preferably, it is 180 degrees or less. As the heat medium flowing through the pressure roller 41, water, oil, or the like can be preferably used.

  The winding unit 5 includes a third rotating shaft 51 for winding the polymer electrolyte fuel cell member 8 in a roll shape, and a third drive mechanism for rotating the third rotating shaft 51.

  Next, a method for producing a polymer electrolyte fuel cell member using the thus constructed apparatus for producing a polymer electrolyte fuel cell member will be described.

  First, as shown in FIG. 1, the electrolyte membrane 6 is unwound from the electrolyte membrane supply unit 2, and the transfer sheet 7 is unwound from each transfer sheet supply unit 3. At this time, each transfer sheet 7 is oriented so that the edge seal 72 and the catalyst layer 73 face the electrolyte membrane 6, and the catalyst layer 73 of the transfer sheet 7 disposed on the upper side through the electrolyte membrane 6 It arrange | positions so that the position with the catalyst layer 73 of the transfer sheet 7 arrange | positioned on the lower side may correspond. The electrolyte membrane 6 and the transfer sheet 7 unwound in this manner are added by passing between the pair of pressure rollers 41 in a state where the transfer sheet 7, the electrolyte membrane 6 and the transfer sheet 7 overlap in this order. Pressure is applied by the pressure roller 41. As a result, each transfer sheet 7 is temporarily attached to the electrolyte membrane 6 to form a polymer electrolyte fuel cell member 8. The pressure at this time is not particularly limited as long as the pressure is such that the transfer sheet 7 is temporarily attached to the electrolyte membrane 6 by the adhesive force of the edge seal 72 itself, but is about 0.5 to 20 MPa. It is preferable that the pressure is about 1 to 10 MPa. At this time, the pressure roller 41 may be heated. In this case, the surface temperature of the pressure roller 41 is preferably about 200 degrees or less, and more preferably about 180 degrees or less.

  As shown in FIG. 4, the solid polymer fuel cell member 8 formed as described above is configured by temporarily attaching a transfer sheet 7 to each of an upper surface and a lower surface of a long electrolyte membrane 6. ing. The polymer electrolyte fuel cell member 8 configured in this way is rolled up by being wound around the winding unit 5.

  Next, a method of forming a polymer electrolyte fuel cell from the polymer electrolyte fuel cell member 8 formed in a roll shape will be described with reference to FIG. First, the roll-shaped polymer electrolyte fuel cell member 8 is taken out from the winding unit 5 and is cut between the catalyst layers 73 by a known cutting device to form a polymer electrolyte fuel cell member for each single cell. 8 ′ is produced (FIG. 5A). Then, the solid polymer fuel cell member 8 ′ for each single cell is heated and pressurized by a hot press machine to transfer the edge seal 72 and the catalyst layer 73 to the electrolyte membrane 6. As a condition for hot pressing at this time, the pressure level is preferably about 0.5 to 20 MPa, more preferably about 1 to 10 MPa in order to avoid transfer failure. The heating temperature is preferably about 200 ° C. or less, and more preferably about 150 ° C. or less in order to avoid breakage or deformation of the electrolyte membrane. In addition, the order of this cutting process and hot pressing may be reversed.

  The base material 71 is peeled from the solid polymer fuel cell member 8 ′ thus formed to form the edge-sealed catalyst layer-electrolyte membrane laminate 10 (FIG. 5B). Then, the conductive porous base material 9 is laminated on each catalyst layer 73 of the catalyst layer-electrolyte membrane laminate 10 with edge seal to form the electrode-electrolyte membrane laminate 20 with edge seal (FIG. 5 (c). )). The conductive porous substrate 9 is preferably the same size as the catalyst layer 73 to be laminated. Moreover, the catalyst layer-electrolyte membrane laminate 10 with an edge seal can be protected by the substrate 71 by not peeling the substrate 71 until immediately before the conductive porous substrate 9 is laminated.

  Finally, a frame-like gasket 11 is arranged on the edge seal 72 so as to surround the conductive porous substrate 9, and a separator 12 in which a gas flow path 121 is formed is arranged so as to be sandwiched from above and below to form a solid polymer. The fuel cell 30 is completed (FIG. 5D).

  Next, the material of each element of the polymer electrolyte fuel cell described above will be described.

  The electrolyte membrane 6 is formed, for example, by applying a solution containing a hydrogen ion conductive polymer electrolyte on a substrate and drying it. Examples of the hydrogen ion conductive polymer electrolyte include a perfluorosulfonic acid-based fluorine ion exchange resin, more specifically, a perfluorocarbonsulfonic acid-based resin in which the C—H bond of a hydrocarbon ion-exchange membrane is substituted with fluorine. Examples include polymers (PFS polymers). By introducing a fluorine atom having high electronegativity, it is chemically very stable, the dissociation degree of the sulfonic acid group is high, and high ion conductivity can be realized. Specific examples of such a hydrogen ion conductive polymer electrolyte include “Nafion” (registered trademark) manufactured by DuPont, “Flemion” (registered trademark) manufactured by Asahi Glass Co., Ltd., and “Aciplex” manufactured by Asahi Kasei Corporation. ”(Registered trademark),“ Gore Select ”(registered trademark) manufactured by Gore, and the like. The concentration of the hydrogen ion conductive polymer electrolyte contained in the hydrogen ion conductive polymer electrolyte-containing solution is usually about 5 to 60% by weight, preferably about 20 to 40% by weight. In addition to the above electrolyte membrane made of a hydrogen ion conductive polymer electrolyte, an anion conductive polymer electrolyte membrane and a liquid substance-impregnated membrane can also be mentioned. An anion conductive polymer electrolyte membrane is formed by applying a solution containing an anion conductive polymer electrolyte on a substrate and drying, and this anion conductive polymer electrolyte is a hydrocarbon-based one. Examples of the hydrocarbon-based resin include Aciplex (registered trademark) A201, 211,221 manufactured by Asahi Kasei Corporation, and Neocepta (registered trademark) manufactured by Tokuyama Corporation. AM-1, AHA, and the like, and examples of the fluorine-based resin include Tosflex (registered trademark) IE-SF34 manufactured by Tosoh Corporation. Examples of the liquid substance-impregnated film include polybenzimidazole (PBI) impregnated with phosphoric acid.

  The substrate 71 of the transfer sheet 7 is not particularly limited as long as it is in the form of a sheet or film, and examples thereof include a metal foil and a polymer film. In addition to these, coated paper such as art paper, coated paper, and light coated paper, and non-coated paper such as notebook paper and copy paper may be used. Moreover, in order to improve the peelability from the edge seal 72 or the catalyst layer 73, a release layer or the like may be provided. As the release layer, for example, a surface composed of a known wax or a fluororesin can be provided on the surface of the base 71 by coating, but a vapor deposition layer made of silicon oxide or the like is provided as a release layer. Is desirable. Polymer films include polyimide, polyethylene terephthalate (PET), polyparvanic acid aramid, polyamide (nylon), polysulfone, polyethersulfone, polyphenylene sulfide, polyether ether ketone, polyetherimide, polyarylate, polyethylene naphthalate. A phthalate etc. are mentioned. In addition, polyethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroperfluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE) It is also possible to use a heat-resistant fluororesin such as The thickness of the substrate 71 is usually about 6 to 100 μm, preferably about 10 to 30 μm, from the viewpoints of handleability and economy. As such a base material 71, a polymer film which is inexpensive and easily available is preferable, and polyethylene terephthalate or the like is more preferable.

  Examples of the catalyst layer 73 include those containing carbon particles carrying catalyst particles and a hydrogen ion conductive polymer electrolyte. As the hydrogen ion conductive polymer electrolyte, “Nafion” (registered trademark) manufactured by DuPont, the same as the electrolyte of the electrolyte membrane 6, “Flemion” (registered trademark) manufactured by Asahi Glass Co., Ltd., manufactured by Asahi Kasei Co., Ltd. "Aciplex" (registered trademark), "Gore Select" (registered trademark) manufactured by Gore, Inc., and the like. The concentration of the hydrogen ion conductive polymer electrolyte contained in the hydrogen ion conductive polymer electrolyte-containing solution is usually about 5 to 60% by weight, preferably about 20 to 40% by weight. In addition to the hydrogen ion conductive polymer electrolyte, an anion conductive polymer electrolyte is also included. Examples of the anion conductive polymer electrolyte include hydrocarbon resins and fluorine resins. Specific examples of the hydrocarbon resins include Aciplex (registered trademark) A201, 2111, 221 manufactured by Asahi Kasei Corporation, Examples include Neocepta (registered trademark) AM-1, AHA manufactured by Tokuyama Corporation, and examples of the fluorine-based resin include Tosflex (registered trademark) IE-SF34 manufactured by Tosoh Corporation. Moreover, as a catalyst particle, platinum, a platinum compound, etc. are mentioned, for example. 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. In general, the catalyst particles contained in the cathode catalyst layer are platinum, and the catalyst particles contained in the anode catalyst layer are an alloy of the metal and platinum. The carbon particles are not limited as long as they have electrical conductivity, and known or commercially available carbon particles can be widely used. For example, carbon black, graphite, activated carbon, or the like can be used alone or in combination. Examples of carbon black include channel black, furnace black, ketjen black, acetylene black, and lamp black. The arithmetic average particle diameter of the carbon particles is usually about 5 nm to 200 nm, preferably about 20 to 80 nm. The average particle size of the carbon particles can be measured by, for example, a particle size distribution measuring device LA-920: manufactured by Horiba, Ltd.

  The material of the edge seal 72 is preferably a polyolefin resin, for example, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α / olefin copolymer, polypropylene, polybutene, polyisobutene, poisobutylene, polybutadiene, Polyisoprene, ethylene-methacrylic acid copolymer, ethylene-unsaturated carboxylic acid copolymer such as ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ionomer resin, ethylene-vinyl acetate copolymer A polymer etc. can be used. In addition, acid-modified polyolefin resins and silane-modified polyolefin resins modified with them can be used. Among them, it is insulating to use polypropylene modified with unsaturated carboxylic acid or polyethylene modified with unsaturated carboxylic acid. From the viewpoint of heat resistance and weak adhesion to the substrate 71. In addition, other materials similar to the electrolyte membrane 6 such as perfluorocarbon sulfonic acid-based fluorine ion exchange resin can be mentioned. Specifically, “Nafion” (registered trademark) manufactured by DuPont, Asahi Glass Co., Ltd. “Flemion” (registered trademark) manufactured by Asahi Kasei Co., Ltd., “Aciplex” (registered trademark) manufactured by Asahi Kasei Co., Ltd., “Gore Select” (registered trademark) manufactured by Gore, Inc., and the like. An example of a manufacturing method of the edge seal 72 will be described. The edge seal 72 can be manufactured by bringing the above-described material into a molten state, extruding the material by a melt extrusion method, and providing a desired opening. The method for forming the opening is not limited, but the opening can be formed by cutting using a Thomson blade or the like. In addition, you may provide the well-known easy-adhesion process for improving the adhesiveness with the electrolyte membrane 6 or the base material 71, and a well-known adhesive layer on the surface of the edge seal 72 as needed.

  Here, although the manufacturing method of the said transfer sheet 7 is demonstrated, it is not limited to the method described below. First, the catalyst layer 73 is formed on the base material 71. Specifically, the above-described carbon particles supporting the catalyst particles and the hydrogen ion conductive polymer electrolyte are mixed and dispersed in an appropriate solvent to prepare a catalyst paste. Then, the catalyst layer 73 is formed by coating and drying the catalyst paste on the base material 71 so that the formed catalyst layer has a desired film thickness and a desired shape. In addition, the catalyst layer 73 can be made into a desired shape by performing coating through a mask in which openings having a desired shape are formed or by performing pattern coating. If necessary, each catalyst paste is applied onto the base material 71 through a release layer. Thereby, the releasability from the catalyst layer 73 of the base material 71 can be further improved. Moreover, as a coating method of a catalyst paste, well-known coating methods, such as screen printing, spray coating, die coating, knife coating, can be mentioned. After applying the catalyst paste, the catalyst layer 73 is formed on the substrate 71 by drying at a predetermined temperature and time. 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 10 minutes to 1 hour. In addition, as a solvent used for the said catalyst paste, various alcohols, various ethers, various dialkyl sulfoxides, water, or these mixtures etc. are mentioned, Among these, alcohol is preferable. Examples of alcohols include monohydric alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol, and various polyhydric alcohols. On the base material 71 on which the catalyst layer 73 is thus formed, an edge seal 72 having an opening having the same shape as the catalyst layer 73 is adhered. At this time, the edge seal 72 is bonded onto the base material 71 so that the catalyst layer 73 is accommodated in the opening. This adhesion can be based on the adhesiveness of the edge seal 72 itself.

  The thickness of the catalyst layer 73 and the edge seal 72 is preferably substantially the same. Specifically, when the thickness of the edge seal 72 is 100%, the ratio of the difference in thickness between the edge seal 72 and the catalyst layer 73 is It is preferably within ± 20%, and more preferably within ± 5%. By making the thicknesses of the catalyst layer 73 and the edge seal 72 substantially the same, it is possible to prevent the membrane of the electrolyte membrane 6 from being thin and wrinkled in the above-described hot pressing step between the transfer sheet 7 and the electrolyte membrane 6. Further, it is preferable that there is no gap between the catalyst layer 73 and the edge seal 72. Even when a gap is generated due to the accuracy in forming the catalyst layer 73 and the edge seal 72, it is preferable that the edge seal 72 is melted and bonded to the catalyst layer 73 by hot pressing. Specifically, the gap is about 2 mm. Is preferably within 1 mm, and more preferably within about 1 mm.

  The conductive porous substrate 9 is composed of a porous conductive substrate in order to efficiently supply fuel gas and oxidant gas as fuel to the catalyst layer. Such a conductive porous substrate 9 As the base material 9, it is well-known and the various electroconductive porous base materials which comprise an anode (fuel electrode) and a cathode can be used. Examples of such a conductive porous substrate 9 include carbon paper and carbon cloth.

  As the gasket 11, it is possible to use a gasket that has a strength sufficient to withstand hot pressing and has a gas barrier property that does not leak fuel and oxidant to the outside. For example, a polyethylene terephthalate sheet or Teflon ( (Registered trademark) sheet, silicon rubber sheet, and the like.

  The separator 12 is known and may be any conductive plate that is stable even in the environment inside the fuel cell. In general, a carbon plate in which a gas flow path is formed is used. In addition, the separator is made of a metal such as stainless steel, and the surface of the metal is formed with a coating made of a conductive material such as chromium, a platinum group metal or oxide thereof, or a conductive polymer, and the separator is also made of a metal. In addition, it is also possible to use a metal surface plated with a material such as silver, a platinum group composite oxide, or chromium nitride.

  As described above, according to the present embodiment, since the edge seal 72 and the catalyst layer 73 on the base material 71 do not overlap each other, even if the transfer sheet 7 and the electrolyte membrane 6 are overlapped and pressure is applied, the electrolyte membrane 6 The pressure applied to is uniform, and the electrolyte membrane 6 can be prevented from becoming thin locally. Further, since the edge seal 72 has an opening, there is a problem that when the edge seal 72 is tensioned, the shape is twisted or locally extended and deformed. Although it is difficult to handle alone, in the above embodiment, since the edge seal 72 is supported by the base material 71, the handling can be facilitated.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to these, A various change is possible unless it deviates from the meaning of this invention.

  For example, the polymer electrolyte fuel cell produced in the above embodiment uses a long polymer electrolyte fuel cell member wound in a roll shape, but is not particularly limited to this. For example, it may be a sheet-like sheet. In this case, the sheet-like electrolyte membrane 6 and the two transfer sheets 7 are prepared, and the transfer sheet 7, the catalyst layer 73 and the edge seal 72 of each transfer sheet 7 are directed to the electrolyte membrane 6 side, These are overlaid in the order of the electrolyte membrane 6 and the transfer sheet 7. And hot press is performed by the hot press machine similarly to the said embodiment. Thereafter, the polymer electrolyte fuel cell can be produced by the same method as in the above embodiment.

  In the above embodiment, the catalyst layer has the same size on the cathode side and the anode side. However, the catalyst layer can have different sizes. In this case, the catalyst layer on the anode side is more than the catalyst layer on the cathode side. It is preferable to enlarge it. In this case as well, the catalyst layer 73 and the edge seal 72 are in contact with each other without a gap. By forming the anode-side catalyst layer large in this way, the anode-side catalyst layer is surely opposed to the cathode-side catalyst layer via the electrolyte membrane even when misalignment occurs. be able to. For this reason, corrosion of the catalyst layer on the cathode side due to the potential can be prevented. Moreover, deterioration of the electrolyte membrane can be prevented. In addition, since the edge seal and the catalyst layer do not overlap and are in contact with each other without any gaps, even if misalignment occurs, O2 supplied to the cathode does not directly cross leak to the anode, and hydrogen peroxide is generated at the anode. Can be suppressed significantly, and deterioration of the electrolyte membrane can be prevented.

  Further, in the above embodiment, when the transfer sheet 7 is produced, the edge seal 72 is adhered after the catalyst layer 73 is formed on the base material 71, but this may be reversed. That is, first, an edge seal 72 having an opening formed thereon is bonded onto the base material 71, and then a catalyst paste is applied and dried onto the base material 71 through the opening of the edge seal 72 to form a catalyst. The transfer sheet 7 may be produced by forming the layer 73. More specifically, as shown in FIG. 6, a mask 74 composed of a release layer 741 and a mask main body 742 is prepared (FIG. 6A), and an edge seal 72 is bonded to the mask 74 to mask it. The attached edge seal 75 is produced (FIG. 6B). And the opening part 751 is formed in this edge seal 75 with a mask (FIG.6 (c)), and the base material 71 is adhere | attached on the edge seal 72 side (FIG.6 (d)). Then, after applying the catalyst paste from the mask 74 side to the base material 71 to which the edge seal 75 with the mask is adhered and drying it (FIG. 6E), the mask 74 is peeled off and the transfer sheet 7 is peeled off. Is completed (FIG. 6F). In addition, this catalyst paste may be applied to the whole from the mask 74 side, or pattern coating can be performed aiming at the opening 751. In addition, an edge seal 72 having an opening formed on the base 71 is formed without using the mask 74 itself, and intermittently formed on the base 71 exposed from the opening of the edge seal 72. The catalyst layer 73 can also be formed by coating.

  Further, in the above embodiment, the transfer sheet 7 is formed by arranging the catalyst layers 73 in a line in the longitudinal direction. However, as shown in FIG.

  Further, in the above embodiment, the transfer sheet 7 is temporarily attached to the electrolyte membrane 6 by pressurization by the pressurization unit 4, and after winding it once by the winding unit 5, the electrolyte membrane is performed by hot pressing. 6, the edge seal 72 and the catalyst layer 73 of the transfer sheet 7 are transferred to the electrolyte film 6, for example, by performing hot pressing in the pressurizing unit 4. Can also be transferred.

  In the above embodiment, the transfer sheet 7 is temporarily attached to both surfaces of the electrolyte membrane 6. However, the transfer sheet 7 can be formed only on one surface of the electrolyte membrane 6.

  Further, in the above embodiment, the electrolyte membrane 6 is sent out by rotating the first rotating shaft 21 by the first driving mechanism, and rotates the third rotating shaft 51 by the third driving mechanism of the winding unit 5. However, the method of transporting the electrolyte membrane 6 is not limited to this. For example, the first driving mechanism is omitted and the first rotating shaft 21 is configured to freely rotate, and the electrolyte membrane 6 is transported only by winding by the rotation of the third rotating shaft 51 by the third driving mechanism. It can also be configured. Similarly, the transfer sheet 7 is also transported by omitting the second drive mechanism and freely rotating the second rotation shaft, and only winding by rotation of the third rotation shaft 51 by the third drive mechanism. Can also be done.

  The present invention will be described more specifically with reference to the following examples and comparative examples. In addition, this invention is not limited to the following Example.

Example 1
The electrolyte membrane 6 is an NRE212CS having a film thickness of 53 μm cut to a size of 63 × 63 mm.
(Dupont) was used.

  Next, the transfer sheet 7 was produced in the following manner. First, 2 g of platinum catalyst-supported carbon (platinum supported amount: 45.7 wt%, manufactured by Tanaka Kikinzoku Co., Ltd., TEC10E50E), 1 g of 1-butanol, 10 g of 3-butanol, 20 g of a fluororesin (5 wt% Nafion binder, manufactured by DuPont) and 6 g of water was added, and these were stirred and mixed with a disperser to prepare a catalyst paste.

  Next, a polyester film provided with a vapor deposition layer made of silicon oxide was prepared as the base material 71, and a polyester film mask having an opening of 50 × 50 mm was placed on the base material 71. Then, the catalyst paste is coated and dried on the base material 71 through the opening of the mask so that the thickness of the catalyst layer after drying the catalyst layer becomes 20 μm, and the mask is peeled off. A catalyst layer 73 was produced.

  Subsequently, the unsaturated carboxylic acid graft-modified polypropylene was extruded at a thickness of 20 μm by a melt extrusion method, and an edge seal 72 was formed. The edge seal 72 was cut to a size of 63 × 63 mm, and an opening having a size of 50 × 50 mm was formed at the center. And the edge seal 72 was arrange | positioned on the base material 71 so that the catalyst layer 73 might be settled in an opening part, and the transfer sheet 7 was produced.

  The transfer sheet 7 is arranged on both surfaces of the electrolyte membrane 6 so that the catalyst layer 73 and the edge seal 72 face the electrolyte membrane 6 side, and the catalyst layers of the transfer sheets 7 are aligned via the electrolyte membrane 6. Aligned. And the catalyst layer 73 was formed on both surfaces of the electrolyte membrane 6 by heat-pressing on conditions of 135 degreeC, 5.0 Mpa, and 150 second, and the catalyst layer-electrolyte membrane laminated body 10 with an edge seal was produced.

  Subsequently, carbon paper (TGP-H-090, manufactured by Toray Industries Inc., thickness) cut into a size of 50 × 50 mm as the conductive porous substrate 9 on the catalyst layer 73 exposed from the opening. 280 μm) was laminated to form an electrode-electrolyte membrane laminate 20 with edge seal.

(Example 2)
As the electrolyte membrane 6, NRE212CS (manufactured by Dupont) having a film thickness of 53 μm cut to a size of 63 × 63 mm was used.

  Next, the transfer sheet 7 was produced in the following manner. Two types of transfer sheets 7 were prepared: an anode transfer sheet 7a and a cathode transfer sheet 7b.

  First, the anode transfer sheet 7a will be described. A polyester film was prepared as the substrate 71a, and a polyester film mask having an opening of 50 × 50 mm was placed on the substrate 71a. Then, the same catalyst paste as in Example 1 was applied onto the base material 71a through the opening of the mask so that the catalyst layer thickness after drying of the catalyst layer was 16 μm, dried, the mask was peeled off, and the anode A catalyst layer 73a was produced. Then, an unsaturated carboxylic acid graft-modified polyethylene was extruded at a thickness of 20 μm by a melt extrusion method to form an edge seal 72a. This edge seal 72a was cut into a size of 63 × 63 mm, and an opening with a size of 50 × 50 mm was formed at the center. This edge seal 72a was adhered onto the base material 71a so that the catalyst layer 73a was accommodated in the opening, thereby producing an anode transfer sheet 7a.

  Subsequently, a cathode transfer sheet 7b was produced. A polyester film was prepared as the substrate 71b, and a polyester film mask having a 48 × 48 mm opening was placed on the substrate 71b. Then, the catalyst paste was applied onto the base material 71b through the opening of the mask so that the catalyst layer thickness after drying of the catalyst layer was 16 μm, dried, the mask was peeled off, and the cathode catalyst layer 73b was produced. . Further, an edge seal 72b similar to the edge seal 72a of the anode transfer sheet 7a was cut to a size of 63 × 63 mm, and an opening of a size of 48 × 48 mm was formed at the center. Then, the edge seal 72b was adhered onto the base material 71b so that the catalyst layer 73b was accommodated in the opening, thereby preparing the cathode transfer sheet 7b.

  The anode transfer sheet 7 a and the cathode transfer sheet 7 b are arranged on both surfaces of the electrolyte membrane so that the catalyst layer 73 faces the electrolyte membrane 6, and the catalyst layers 73 of the transfer sheets 7 are aligned via the electrolyte membrane 6. Aligned. Then, the anode catalyst layer 73a is formed on one surface of the electrolyte membrane 6 and the cathode catalyst layer 73b is formed on the other surface by hot pressing under conditions of 135 ° C., 5.0 MPa, and 150 seconds. An electrolyte membrane laminate 10 was produced. In the catalyst layer-electrolyte membrane laminate with edge seal, the anode catalyst layer 73a is formed larger than the cathode catalyst layer 73b.

  Furthermore, carbon paper (manufactured by Toray Industries, Inc., TGP-H-) was cut as a conductive porous substrate 9a for the anode onto the anode catalyst layer 73a exposed from the opening. 090, thickness 280 μm). On the cathode catalyst layer 73b exposed from the opening, carbon paper (TGP-H-090, manufactured by Toray Industries, Inc.) cut into a size of 48 × 48 mm is formed as the conductive porous substrate 9b for the cathode. , Thickness 280 μm) was laminated to form an electrode-electrolyte membrane laminate 20 with edge seal.

(Example 3)
As the electrolyte membrane 6, NRE212CS (manufactured by Dupont) having a width of 63 mm, a length of 60 m, and a film thickness of 53 μm wound in a roll shape was used.

Next, the transfer sheet 7 was produced in the following manner. First, as shown in FIG. 6, the mask 74 comprised from the vapor deposition layer 741 which consists of silicon oxides, and the mask main body 742 which consists of a polyester film was prepared (FIG. 6 (a)). The mask 74 has a width of 63 mm and a length of 60 m. An edge seal 72 having a thickness of 25 μm was formed on the mask 74 on the vapor deposition layer 741 side by melt extrusion of an unsaturated carboxylic acid graft-modified polypropylene (FIG. 6B). Then, a plurality of openings 751 each having a size of 50 × 50 mm were formed at the center in the width direction of the edge seal 75 with the mask with an interval d ₁ of 13 mm in the longitudinal direction (FIG. 6C).
Next, a polyester film wound in a roll shape having a width of 63 mm and a length of 60 m is prepared as the base material 71, and roll pressure bonding is performed so that the edge seal 72 side of the edge seal with mask 75 is bonded to the base material 71. This was done (FIG. 6 (d)). Then, the catalyst paste prepared in the same manner as in Example 1 was applied and dried from the mask 74 side of the edge seal 75 with mask joined on the base 71 so that the thickness after drying was 20 μm ( After that, the mask 74 was peeled off to produce a transfer sheet 7 (FIG. 6F).

  The transfer sheet 7 produced as described above is formed into a roll shape, and the roll-shaped transfer sheet 7 is set on the second rotating shaft 31 of the transfer sheet supply unit 3 as shown in FIG. The first rotating shaft 21 of the supply unit 2 was set. Then, the first and second rotating shafts 21 and 31 are rotated by the first driving mechanism and the second driving mechanism to unwind the electrolyte membrane 6 and the transfer sheet 7 so that the centers of the catalyst layers 73 are aligned. Each transfer sheet 7 was placed and sent out by a roll. Then, heat and pressure bonding was performed with a pressure roll 41 heated to 110 ° C., and the transfer sheet 7 was adhered to both surfaces of the electrolyte membrane 6 to produce a solid polymer fuel cell member 8. The pressure at this time was 3 MPa.

  Subsequently, the long polymer electrolyte fuel cell member 8 produced as described above is cut at intervals of 63 mm between the catalyst layers 73 to obtain a sheet-like solid polymer fuel cell member 8 ′. Produced. The sheet-like solid polymer fuel cell member 8 ′ is hot-pressed from both sides under the conditions of 135 ° C., 5.0 MPa, and 150 seconds, whereby the edge seal 72 and the catalyst layer 73 are formed on both sides of the electrolyte membrane 6. Was transferred and formed.

  Then, the base material 71 is peeled from the solid polymer fuel cell member 8 ′, and the conductive porous base material 9 is formed in a size of 50 × 50 mm on the catalyst layer 73 exposed from the opening. Cut carbon paper (manufactured by Toray Industries, Inc., TGP-H-090, thickness 280 μm) was laminated to form an electrode-electrolyte membrane laminate 20 with an edge seal.

Example 4
An electrode-electrolyte membrane laminate 20 with an edge seal was formed in the same manner as in Example 3 except that the coating method of the catalyst paste was different. The catalyst paste was applied in a pattern from the mask 74 side of the edge seal 75 with mask joined on the base material 71 so that the thickness after drying was only 20 μm on the base material 71 exposed from the opening. did.

(Example 5)
As the electrolyte membrane 6, NRE212CS (manufactured by Dupont) having a width of 63 mm, a length of 60 m, and a film thickness of 53 μm wound in a roll shape was used.

  Next, the transfer sheet 7 was produced in the following manner. Two types of transfer sheets 7 were prepared: an anode transfer sheet 7a and a cathode transfer sheet 7b.

  First, the anode transfer sheet 7a will be described. The anode transfer sheet 7a is the transfer sheet of Example 3 except that the thickness of the edge seal 72a is 21 μm and a mat polyester film (Lumirror X44, manufactured by Toray Industries, Inc.) is used as the base material 71a. 7 was produced in the same manner. The cathode transfer sheet 7b has a point that the thickness of the edge seal 72b is 21 μm, the size of the opening of the edge seal 72b is 48 × 48 mm, and a mat polyester film (Lumirror X44, It was produced in the same manner as the transfer sheet 7 of Example 3 except that Toray Industries, Inc. was used.

  An electrode-electrolyte membrane laminate 20 with an edge seal was produced from the electrolyte membrane 6 and the transfer sheet 7 in the same manner as in Example 3. Since the size of the opening of the cathode side edge seal 72b is 48 × 48 mm, the size of the cathode side catalyst layer 73b and the conductive porous substrate 9b is 48 × 48 mm.

(Comparative Example 1)
The size of the catalyst layer is a catalyst paste adjusted in the same manner as in Example 1 from the point that the opening of the edge seal is 60 × 60 mm and the mask 74 side of the edge seal 75 with mask joined on the base 71. A membrane electrode assembly with an edge seal was formed in the same manner as in Example 3 except that the coating was dried by intermittent coating so that the thickness after drying was 50 μm and 20 μm.

(Evaluation method)
About the electrode-electrolyte membrane laminated body with an edge seal | sticker of Examples 1-5 and the comparative example 1, the gasket 11 and the separator 12 were installed, the polymer electrolyte fuel cell 30 was each produced, and the load fluctuation cycle test was implemented. The measurement conditions at this time were a cell temperature of 80 ° C., a fuel utilization rate of 70%, an oxidant utilization rate of 40%, and a humidification temperature of 50 ° C. In the load fluctuation cycle test, a cycle in which power was generated for 1 minute at a current density of 0.3 A / cm 2 and then power was generated for 1 minute at a current density of 0.01 A / cm 2 was repeated. As a result of the load fluctuation cycle test, the voltage of the fuel cells of Examples 1 to 5 did not decrease even after 1500 hours. Moreover, when the electrolyte membrane was confirmed after this load fluctuation | variation cycle test, the damage of the electrolyte membrane was not seen in all the Examples. On the other hand, in the polymer electrolyte fuel cell of Comparative Example 1, the voltage dropped when 300 hours passed, and the electrolyte membrane was confirmed to be broken.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus of member for polymer electrolyte fuel cells 2 Electrolyte membrane supply part 3 Transfer sheet supply part 4 Pressurization part 6 Electrolyte film 7 Transfer sheet 71 Base material 72 Edge seal 73 Catalyst layer 8 Member for polymer electrolyte fuel cell

Claims (9)

An electrolyte membrane supplying step for supplying an electrolyte membrane;
An edge seal having an opening is bonded onto the substrate, the transfer sheet producing step of producing a transfer sheet by forming a catalyst layer on the substrate on within the opening in the edge seal,
And two supply the transfer sheet supply step pre Symbol transfer sheet,
An arrangement step of arranging one of the transfer sheets on one surface of the electrolyte membrane such that the edge seal and the catalyst layer face the electrolyte membrane;
An arrangement step of arranging the other of the transfer sheet on the other surface of the electrolyte membrane so that the edge seal and the catalyst layer face the electrolyte membrane;
A pressing step for applying pressure so that an edge seal and a catalyst layer of the transfer sheet adhere to the electrolyte membrane;
A method for producing a member for a polymer electrolyte fuel cell, comprising: An electrolyte membrane supplying step for supplying a long electrolyte membrane;
The edge seal elongate plurality of openings arranged in the longitudinal direction is formed is bonded onto a long base material, transfer by forming a catalyst layer on the substrate on within the respective openings of the edge seal A transfer sheet production process for producing a sheet;
And two supply the transfer sheet supply step pre Symbol transfer sheet,
An arrangement step of arranging one of the transfer sheets on one surface of the electrolyte membrane so that the edge seal and each catalyst layer face the electrolyte membrane;
An arrangement step of arranging the other of the transfer sheet on the other surface of the electrolyte membrane so that the edge seal and the catalyst layer face the electrolyte membrane;
A pressing step for applying pressure so that an edge seal and a catalyst layer of the transfer sheet adhere to the electrolyte membrane;
A method for producing a member for a polymer electrolyte fuel cell, comprising: In the electrolyte membrane supply step, the electrolyte membrane is conveyed in the longitudinal direction,
In the transfer sheet supply step, the transfer sheet is conveyed in the same direction as the electrolyte membrane,
3. The production of a polymer electrolyte fuel cell member according to claim 2 , wherein in the pressing step, the transfer sheet is adhered to the electrolyte membrane by sandwiching the electrolyte membrane being transferred and the transfer sheet between a pair of rollers. Method. The method for producing a member for a polymer electrolyte fuel cell according to claim 2 or 3 , further comprising a step of cutting the long electrolyte membrane to which the transfer sheet is bonded between the openings. The transfer sheet manufacturing step includes
Adhering an edge seal to a mask to produce an edge seal with a mask;
Forming the opening in the edge seal with mask, and bonding the base material to the edge seal side;
The manufacturing method of the member for polymer electrolyte fuel cells in any one of Claims 1-4 containing this. The transfer sheet manufacturing step includes
A step of applying a catalyst paste from the mask side to the base material to which the edge seal with a mask having the opening is adhered,
Peeling the mask;
The manufacturing method of the member for polymer electrolyte fuel cells of Claim 5 containing this. A method for producing a polymer electrolyte fuel cell member according to claim 1 or 4 ,
Peeling the base material of the transfer sheet ;
The manufacturing method of the catalyst layer-electrolyte membrane laminated body with an edge seal | sticker containing this. A method for producing a catalyst layer-electrolyte membrane laminate with an edge seal according to claim 7 ,
Further comprising, et Jjishiru with electrode laminating a conductive porous substrate on the catalyst layer - the manufacturing method of the electrolyte membrane laminate. Edge seals catalyst layer according to claim 7 - membrane laminate manufacturing process or edge seals electrode according to claim 8 - to the manufacturing method of the electrolyte membrane laminate,
Installing a gasket on the edge seal;
Sandwiching the electrode-electrolyte membrane laminate with an edge seal provided with the gasket from both sides with a separator;
A method for producing a polymer electrolyte fuel cell, comprising:

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