JP2010182563A - Device and method for manufacturing membrane catalyst layer assembly, as well as device and method for manufacturing membrane electrode assembly - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device and method for manufacturing a membrane catalyst layer assembly, and a device and method for manufacturing a membrane electrode assembly, capable of reducing peeling failure. <P>SOLUTION: A manufacturing device 1 for the membrane catalyst layer assembly having a catalyst layer 112 on both sides of an electrolyte membrane 10 includes an electrolyte membrane conveying part 2 to convey a lengthy electrolyte membrane 10, a catalyst layer transcription sheet conveying part 3 to convey a lengthy catalyst transcription sheet 11 having the catalyst layer 112 on a base material sheet 111 to the same direction as that of the electrolyte membrane 10 on the electrolyte membrane 10, a heat press part 4 to pressurize against the electrolyte membrane 10 while heating the catalyst layer transcription sheet 11, and a peeling part 6 installed at the downstream of the hot press part 4 and exfoliating the base material sheet 111 while heating the electrolyte membrane 10 and the catalyst layer transcription sheet 11. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a manufacturing apparatus and manufacturing method for a membrane catalyst layer assembly, and a manufacturing apparatus and manufacturing method for a membrane electrode assembly.

  A fuel cell is a cell in which electrodes are arranged on both sides of an electrolyte and generates electricity by an electrochemical reaction between hydrogen and oxygen, and only water is generated during power generation. Thus, unlike the conventional internal combustion engine, it is expected to spread as a next-generation clean energy system because it does not generate environmental load gas such as carbon dioxide. In particular, the polymer electrolyte fuel cell has a low operating temperature and low electrolyte resistance. In addition, it uses a highly active catalyst, so it can obtain high output even in a small size. Is expected to be put to practical use.

  In this polymer electrolyte fuel cell, a catalyst layer and a gas diffusion layer that are slightly smaller than the electrolyte membrane are sequentially laminated on both surfaces of a proton conductive solid polymer electrolyte membrane. A catalyst layer formed on both sides of the electrolyte membrane (that is, the layer structure is catalyst layer / electrolyte membrane / catalyst layer) is called a membrane-catalyst layer assembly (CCM), and the catalyst is formed on both sides of the electrolyte membrane. An electrode formed of a layer and a gas diffusion layer (that is, a layer structure of gas diffusion layer / catalyst layer / electrolyte membrane / catalyst layer / gas diffusion layer) is referred to as a membrane electrode assembly (MEA). .

  As a method of manufacturing the membrane catalyst layer assembly or the membrane electrode assembly, a so-called coating method is generally adopted in which a catalyst layer paste for forming a catalyst layer is applied and dried on both surfaces of an electrolyte membrane. . However, when the catalyst paste is applied to the electrolyte membrane by this method, the electrolyte membrane is swollen and deformed by a solvent such as water or alcohol contained in the catalyst paste, and it is difficult to form a desired catalyst layer on the electrolyte membrane surface. There is a problem of becoming. Further, in the step of drying the catalyst paste applied to the electrolyte membrane, the electrolyte membrane is exposed to a high temperature, so that the electrolyte membrane undergoes thermal expansion and the like, causing a problem of deformation.

  In order to solve the problem due to the coating method, a catalyst layer transfer sheet having a catalyst layer formed on a base sheet is used, and the catalyst layer transfer sheet and the electrolyte membrane are overlaid and subjected to hot pressing to thereby form a catalyst layer. A so-called transfer method has been proposed in which a film is transferred to an electrolyte membrane (for example, Patent Documents 1 and 2). This method solves the problem of the coating method and has been put to practical use because it is a simple method.

Japanese Patent Laid-Open No. 10-64574 Japanese Patent No. 3465656

  By the way, in the transfer method as described above, it is necessary to peel off the substrate sheet after transferring the catalyst layer to the electrolyte membrane. When the substrate sheet is peeled off, the catalyst layer does not remain on the electrolyte membrane side. There is a problem that a so-called peeling failure occurs such as peeling with the material sheet.

  Then, this invention makes it a subject to provide the apparatus and method for manufacturing a membrane catalyst layer assembly and the apparatus and method for manufacturing a membrane electrode assembly which can reduce peeling defect. .

  As a result of intensive studies on the cause of defective peeling in a conventional method for producing a membrane catalyst layer assembly by a transfer method, the following has been found to be a cause of defective peeling. That is, when the catalyst layer transfer sheet and the electrolyte membrane are heated and pressurized to transfer the catalyst layer to the electrolyte membrane, the electrolyte membrane thermally expands, but the electrolyte membrane is cooled until the subsequent substrate sheet is peeled off. Then, the electrolyte membrane may shrink once. It has been found that when the electrolyte membrane shrinks in this way, the catalyst layer may be peeled off from the electrolyte membrane, which causes a peeling failure. On the other hand, the method for producing a membrane catalyst layer assembly according to the present invention is a method for producing a membrane catalyst layer assembly in which a catalyst layer is formed on at least one surface of an electrolyte membrane, and comprises a long electrolyte membrane. A step of conveying, a step of conveying a long catalyst layer transfer sheet having a catalyst layer formed on a base material sheet in the same direction as the electrolyte membrane on at least one surface of the electrolyte membrane, and the catalyst layer transfer Pressing the electrolyte membrane while heating the sheet so that the catalyst layer is transferred to the electrolyte membrane; and after the catalyst layer is transferred to the electrolyte membrane, the electrolyte membrane and the catalyst layer transfer sheet are Peeling the substrate sheet while heating.

  According to the method for producing a membrane / catalyst layer assembly, the base material sheet is peeled off while heating the electrolyte membrane and the catalyst layer transfer sheet in the peeling step. For this reason, even when the electrolyte membrane is cooled and contracted after the heating and pressurizing step for transferring the catalyst layer to the electrolyte membrane, and the catalyst layer is separated from the catalyst layer, the electrolyte membrane is stretched by heating again and the catalyst layer is It is joined again to the electrolyte membrane. Thereby, the trigger part of peeling defect can be reduced and by extension, peeling defect can be reduced. In the above step, the catalyst layer may be formed only on one surface of the electrolyte membrane, or the catalyst layer may be formed on both surfaces of the electrolyte membrane.

  The peeling process of the said method can peel a base material sheet | seat, heating an electrolyte membrane and a catalyst layer transfer sheet with a peeling roll. In addition, instead of peeling the base sheet while heating with the peeling roll, the process from the heating and pressing step for transferring the catalyst layer to the peeling step may be performed at a glass transition temperature ± 50 ° C. of the electrolyte membrane. Good. Thus, by setting the glass transition temperature ± 50 ° C. of the electrolyte membrane from the heating and pressurizing step to the peeling step, it is possible to prevent the electrolyte membrane from shrinking and more effectively reduce the peeling failure. Can do. Furthermore, while heating the electrolyte membrane and the catalyst layer transfer sheet with a peeling roll, the heating and pressing step to the peeling step can be performed at the above temperature.

  Further, a step of pressing the catalyst layer transfer sheet against the electrolyte membrane may be further included between the heating and pressurizing step and the peeling step. Thereby, a catalyst layer can be joined to an electrolyte membrane more firmly. In addition, it is preferable to perform this press process, heating a catalyst layer transfer sheet.

  Moreover, the process of cooling a membrane catalyst layer assembly may be further included after a peeling process. Thereby, when the membrane-catalyst layer assembly is wound up, it is possible to prevent the catalyst layer from being joined to other portions.

  Further, in the peeling step, it is preferable that the direction in which the base sheet is peeled forms an angle of about 150 to 180 degrees with the conveying direction of the electrolyte membrane. Peeling defects can be further reduced by peeling the substrate sheet at this angle.

  In addition, a method for producing a membrane electrode assembly according to the present invention includes a method for producing any one of the membrane catalyst layer assemblies described above, and a step of joining a gas diffusion layer on the catalyst layer of the membrane catalyst layer assembly. It is out.

  According to this method, since the manufacturing method of the membrane catalyst layer assembly described above is included, it is possible to reduce peeling defects as described above.

  The apparatus for manufacturing a membrane catalyst layer assembly according to the present invention is an apparatus for manufacturing a membrane catalyst layer assembly in which a catalyst layer is formed on at least one surface of an electrolyte membrane, and transports a long electrolyte membrane. A membrane transport section, a catalyst layer transfer sheet transport section for transporting a long catalyst layer transfer sheet having a catalyst layer formed on a base sheet in the same direction as the electrolyte membrane on the electrolyte membrane, and heating the catalyst layer transfer sheet The heat press part which pressurizes with respect to an electrolyte membrane, and the peeling part which is installed in the downstream of the said heat press part and peels a base material sheet | seat, heating an electrolyte membrane and a catalyst layer transfer sheet is provided.

  According to the apparatus for manufacturing a membrane / catalyst layer assembly, the base material sheet is peeled off while heating the electrolyte membrane and the catalyst layer transfer sheet at the peeling portion where the base material sheet is peeled off. For this reason, even when the electrolyte membrane is cooled and contracted while being transported from the hot press portion to the peeling portion, the electrolyte membrane once shrunk by heating again is stretched and the catalyst layer Can be bonded to the electrolyte membrane. For this reason, the trigger part of peeling defect can be reduced and by extension, peeling defect can be reduced.

  The manufacturing apparatus can take various configurations. For example, the peeling part is a pair of peeling rolls arranged so as to sandwich the electrolyte membrane and the catalyst layer transfer sheet, and the peeling roll is the electrolyte membrane and the catalyst layer. You may comprise so that a transfer sheet may be heated. In addition, instead of heating the electrolyte membrane and the catalyst layer transfer sheet with a peeling roll, for example, it is further provided with a high temperature holding means for maintaining the temperature from the hot press portion to the peeling portion at the glass transition temperature ± 50 ° C. of the electrolyte membrane. Further, the electrolyte membrane can be prevented from shrinking, and the peeling failure can be reduced more effectively. Furthermore, you may further provide the said high temperature holding means, heating an electrolyte membrane and a catalyst layer transfer sheet with a peeling roll. The high temperature holding means is configured to have a sealed housing for sealing the space from the hot press part to the peeling part, and a heating means for setting the temperature in the sealed housing to a glass transition temperature ± 50 ° C. of the electrolyte membrane. May be.

  Further, by further comprising a pressurizing means that is installed between the hot press part and the peeling part and pressurizes the catalyst layer transfer sheet against the electrolyte membrane, the catalyst layer is more firmly bonded to the electrolyte membrane. May be. The pressurizing means is preferably configured to heat the catalyst layer transfer sheet.

  Moreover, you may comprise the said heat press part with the heating roll installed so that an electrolyte membrane and a catalyst layer transfer sheet may be pinched | interposed.

  In addition, it is possible to prevent the catalyst layer from being joined to other parts when winding the membrane catalyst layer assembly by further including a cooling unit that is installed downstream of the peeling portion and cools the membrane catalyst layer assembly. it can.

  Moreover, in order to further reduce the peeling failure, it is preferable that the peeling portion guides the base sheet so that the peeling direction forms an angle of 150 to 180 degrees with the transport direction of the electrolyte membrane.

  Further, a membrane electrode assembly manufacturing apparatus according to the present invention includes any one of the above membrane catalyst layer assembly manufacturing apparatus and a gas diffusion unit that is installed downstream of the peeling portion and bonds a gas diffusion layer on the catalyst layer. A layer bonding means.

  According to this manufacturing apparatus, since the apparatus for manufacturing the membrane-catalyst layer assembly is provided, it is possible to reduce peeling defects as described above.

  According to the apparatus and method for manufacturing the membrane catalyst layer assembly and the apparatus and method for manufacturing the membrane electrode assembly according to the present invention, it is possible to reduce peeling defects.

It is the schematic which shows embodiment of the manufacturing apparatus of the membrane catalyst layer assembly which concerns on this invention. It is the schematic which shows other embodiment of the manufacturing apparatus of the membrane catalyst layer assembly based on this invention. It is the schematic which shows embodiment of the manufacturing apparatus of the membrane electrode assembly which concerns on this invention.

  Hereinafter, embodiments of a manufacturing apparatus and a manufacturing method of a membrane catalyst layer assembly according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic view of an apparatus for producing a membrane catalyst layer assembly. In addition, the arrow in a figure has shown the rotation direction of various rolls, and the conveyance direction of various sheets. Further, the left side of FIG. 1 is referred to as “upstream” and the right side is referred to as “downstream”.

  As shown in FIG. 1, the membrane catalyst layer assembly manufacturing apparatus 1 includes an electrolyte membrane transport unit 2 that transports an electrolyte membrane 10 and a catalyst layer transfer sheet 11 in which a catalyst layer 112 is formed on a substrate sheet 111. The catalyst layer transfer sheet transport unit 3 to be transported, the first hot press unit 4 for transferring the catalyst layer 112 of the catalyst layer transfer sheet 11 to the electrolyte membrane 10, and the catalyst layer 112 of the catalyst layer transfer sheet 11 to the electrolyte membrane 10, a second hot press part 5 for bonding more firmly, a peeling part 6 for peeling the substrate sheet 111 after the catalyst layer 112 is transferred to the electrolyte film 10, and a catalyst on both surfaces of the electrolyte film 10. And a cooling unit 7 for cooling the membrane catalyst layer assembly 12 on which the layer 112 is formed.

  The electrolyte membrane transport unit 2 mainly includes an electrolyte membrane supply roll 21 that supplies the electrolyte membrane 10 and a membrane catalyst layer assembly winding roll 22 that winds up the membrane catalyst layer assembly 12. A long electrolyte membrane 10 is set in a roll shape on the electrolyte membrane supply roll 21. Further, the membrane catalyst layer assembly 12 in which the catalyst layers 112 are formed on both surfaces of the electrolyte membrane 10 is wound around the membrane catalyst layer assembly winding roll 22 in a roll shape. Although the conveyance speed of the electrolyte membrane 10 conveyed by this electrolyte membrane conveyance part 2 is not specifically limited, It is preferable to set it as 0.1-5 m / min.

  The catalyst layer transfer sheet conveyance unit 3 includes catalyst layer transfer sheet supply rolls 31 a and 31 b that supply the catalyst layer transfer sheet 11, and base material sheet take-up rolls 32 a and 32 b that take up the base material sheet 111 of the catalyst layer transfer sheet 11. And is composed mainly of. The catalyst layer transfer sheet transport unit 3 is installed above and below the electrolyte membrane transport unit 2 so that the catalyst layer transfer sheet 11 is disposed on the upper and lower surfaces of the electrolyte membrane 10. Each catalyst layer transfer sheet 11 is arranged so that the catalyst layer 112 faces the electrolyte membrane 10 side. The catalyst layer transfer sheet supply rolls 31a and 31b have a long catalyst layer transfer sheet 11 set in a roll shape, and the base sheet take-up rolls 32a and 32b have bases peeled from the catalyst layer transfer sheet 11. The material sheet 111 is wound into a roll shape. The transport speed of the catalyst layer transfer sheet 11 transported by the catalyst layer transfer sheet transport section 3 is not particularly limited, but is preferably the same speed as the electrolyte membrane transport section 2 described above.

  The 1st heat press part 4 is comprised from a pair of heating roll 41a, 41b installed so that the electrolyte membrane 10 and the catalyst layer transfer sheet 11 might be pinched | interposed from the upper and lower sides. The heating rolls 41a and 41b can heat the electrolyte membrane 10 and the catalyst layer transfer sheet 11 by flowing a heat medium therein, and can heat the surface of the heating rolls 41a and 41b to about 200 degrees. It is preferable that heating is performed up to 100 to 180 degrees. As the heat medium flowing in the heating rolls 41a and 41b, water, oil, or the like can be preferably used. Further, the heating rolls 41a and 41b are arranged such that the upper heating roll 41a is counterclockwise and the lower heating roll 41b is rotated so that the electrolyte membrane 10 and the catalyst layer transfer sheet 11 can smoothly flow in the conveyance direction (right direction in FIG. 1). It is rotating clockwise. Moreover, it is preferable to apply a pressure of 0.5 to 20 MPa to the catalyst layer transfer sheet 11 by sandwiching the electrolyte membrane 10 and the catalyst layer transfer sheet 11 with these heating rolls 41a and 41b, and a pressure of 1 to 10 MPa is applied. Is more preferable.

  A second hot press unit 5 is installed downstream of the first hot press unit 4. The second hot press section 5 is also composed of a pair of heating rolls 51a and 51b, similar to the first hot press section 4 described above, and these heating rolls 51a and 51b are arranged from above and below the electrolyte membrane 10 and the catalyst. It is installed so as to sandwich the layer transfer sheet 11. The heating rolls 51a and 51b of the second heat press section 5 can also heat the electrolyte membrane 10 and the catalyst layer transfer sheet 11 by the flow of the heat medium as described above. The pressure applied to the sheet 11 is preferably 1 to 10 MPa.

  A peeling unit 6 is installed downstream of the second hot press unit 5. The peeling unit 6 includes a pair of peeling rolls 61 a and 61 b installed on the upper and lower surfaces of the electrolyte membrane 10 and the catalyst layer transfer sheet 11. The pair of peeling rolls 61a and 61b are arranged such that the peeling roll 61a arranged on the upper side is counterclockwise and guides the peeling of the base sheet 111 of the catalyst layer transfer sheet 11 to the lower side. 61b rotates clockwise. The angle α formed by the transport direction of the electrolyte membrane 10 and the peeling direction of the base sheet 11 at this time is not particularly limited, but is about 150 to 180 degrees in order to further reduce the peeling failure. It is preferable to do. As described above, the roll diameters of the peeling rolls 61a and 61b are reduced, or the winding rolls 32a and 32b for winding the peeled transfer base sheet 111 are arranged on the upstream side. The angle α can be adjusted. The pair of peeling rolls 61a and 61b has a heat medium as described above flowing therein so as to heat the electrolyte membrane 10 at a glass transition temperature ± 50 ° C. of the electrolyte membrane via the catalyst layer transfer sheet 11. The surface temperature of the peeling rolls 61a and 61b is preferably about 200 degrees, more preferably about 100 to 180 ° C. The pressure applied to the catalyst layer transfer sheet 11 by the pair of peeling rolls 61a and 61b is preferably about 0 to 5 MPa.

  A cooling unit 7 is installed downstream of the peeling unit 6. The cooling unit 7 includes a pair of cooling rolls 71 a and 71 b installed on the upper and lower surfaces so as to sandwich the membrane catalyst layer assembly 12. In each of the cooling rolls 71a and 71b, a refrigerant flows inside so as to cool the membrane catalyst layer assembly 12 sandwiched therebetween. It is preferable to cool the membrane catalyst layer assembly 12 to about 50 degrees or less by the cooling rolls 71a and 71b. As the refrigerant, water or the like can be preferably used. The pair of cooling rolls 71a and 71b only need to be in contact with the membrane catalyst layer assembly to such an extent that the membrane catalyst layer assembly can be cooled, and it is not necessary to apply a strong pressure.

  Next, the material of the material constituting the membrane catalyst layer assembly 12 will be described.

  The electrolyte membrane 10 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, the film thickness of the electrolyte membrane 10 is about 20-250 micrometers normally, Preferably it is about 20-80 micrometers. The glass transition temperature (Tg) of the electrolyte membrane 10, that is, the glass transition temperature (Tg) of the perfluorosulfonic acid-based fluorine ion exchange resin is about 110 to 130 ° C. The glass transition temperature can be measured by differential scanning calorimetry or dynamic viscoelasticity measurement.

  The catalyst layer transfer sheet 11 is obtained by forming the catalyst layer 112 on the base sheet 111. Examples of the material of the base sheet 111 include polyimide, polyethylene terephthalate, polyparabanic acid aramid, polyamide (nylon), Examples thereof include polymer films such as polysulfone, polyethersulfone, polyphenylene sulfide, polyether ether ketone, polyetherimide, polyarylate, polyethylene naphthalate, polypropylene, and polyolefin. Further, heat resistance of ethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroperfluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), etc. Fluorine resin can also be used. Further, in addition to the polymer film, coated paper such as art paper, coated paper, and lightweight coated paper, and non-coated paper such as notebook paper and copy paper may be used. The thickness of the base sheet 111 is usually about 6 to 100 μm, preferably about 10 to 30 μm, from the viewpoints of handleability and economy. Therefore, as a base material sheet, an inexpensive and easily available polymer film is preferable, and polyethylene terephthalate or the like is more preferable. Further, a release layer may be formed on the base sheet 111. The release layer can be produced by a known method such as chemical vapor deposition or physical vapor deposition. From the viewpoint of releasability, those made of silicon oxide and formed by chemical vapor deposition are preferred.

  The material of the catalyst layer 112 is a known platinum-containing catalyst layer (cathode catalyst and anode catalyst). Specifically, the catalyst layer 112 contains carbon particles supporting catalyst particles and a hydrogen ion conductive polymer electrolyte. Examples of the catalyst 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. 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. Moreover, as a hydrogen ion conductive polymer electrolyte, the same material as what is used for the electrolyte membrane 10 mentioned above can be used. The thickness of the catalyst layer 112 is preferably 20 to 100 μm in the case of a direct methanol fuel cell, and preferably 15 to 30 μm in the case of a solid polymer fuel cell.

  In the manufacturing method of the catalyst layer transfer sheet 11, first, a base sheet 111 made of the above-described material is prepared. Next, the carbon particles carrying the catalyst particles and the hydrogen ion conductive polymer electrolyte are mixed and dispersed in a suitable solvent to prepare a catalyst paste. Then, the catalyst paste is applied onto the base material sheet 111 through a release layer as necessary according to a known method so that the formed catalyst layer 112 has a desired film thickness. Examples of the method for applying the catalyst paste include known coating methods such as screen printing, spray coating, die coating, and knife coating. After applying the catalyst paste, the catalyst layer 112 is formed on the substrate sheet 111 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. Examples of the solvent used in preparing the catalyst paste include various alcohols, various ethers, various dialkyl sulfoxides, water, or a mixture thereof. Of these, alcohols are 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.

  Next, a method for producing a membrane catalyst layer assembly using the above-described membrane catalyst layer assembly production apparatus 1 will be described.

  First, the electrolyte membrane 10 is unwound from the electrolyte membrane supply roll 21, and the catalyst layer transfer sheet 11 is unwound from the catalyst layer transfer sheet supply rolls 31 a and 31 b, and the upper and lower surfaces of the electrolyte membrane 10 are sandwiched between the catalyst layer transfer sheets 11. Send out downstream in the state. At this time, the catalyst layer transfer sheets 11 laminated on the upper and lower surfaces of the electrolyte membrane 10 are arranged so that the catalyst layer 112 faces the electrolyte membrane 10 side.

  The electrolyte membrane 10 in which the upper and lower surfaces are sandwiched by the catalyst layer transfer sheet 11 is first sent to the first hot press unit 4. The catalyst layer transfer sheet 11 is heated and pressurized by the heating rolls 41 a and 41 b of the first hot press unit 4, whereby the catalyst layer 112 is transferred to the electrolyte membrane 10. Thus, after the catalyst layer 112 is transferred to the electrolyte membrane 10, it is sent to the second hot press unit 5, and the catalyst layer transfer sheet 11 is further heated by the respective heating rolls 51 a and 51 b of the second hot press unit 5. And by being pressurized, the catalyst layer 112 is more firmly joined to the electrolyte membrane 10.

  The electrolyte membrane 10 having the catalyst layer 112 transferred to the upper and lower surfaces in this manner is then sent to the peeling portion 6. In the peeling part 6, the base material sheet 11 is peeled off while heating the electrolyte membrane 10 via the catalyst layer transfer sheet 11 by the peeling rolls 61a and 61b installed up and down, and the peeled upper base material sheet 11 is The lower base sheet 11 is wound around the base sheet take-up roll 32b. When the substrate sheet 11 is peeled in this way, a so-called membrane catalyst layer assembly 12 in which the catalyst layers 112 are formed on the upper surface and the lower surface of the electrolyte membrane 10 is completed.

  The membrane catalyst layer assembly 12 completed as described above is sent to the cooling unit 7, cooled by the pair of cooling rolls 71 a and 71 b, and then wound around the membrane catalyst layer assembly winding roll 22.

  As described above, according to the present embodiment, the base material sheet 111 is peeled off while heating the electrolyte membrane 10 by the peeling rolls 61 a and 61 b of the peeling portion 6. For this reason, even when the electrolyte membrane 10 is cooled and contracted between the first hot press portion 4 and the peeling portion 6 to be separated from the catalyst layer 112, the contracted electrolyte membrane 10 is stretched again. As a result, the catalyst layer 112 is joined, and as a result, the triggering part of the peeling failure can be reduced and the peeling failure can be reduced.

  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, as shown in FIG. 2, a high temperature holding means 8 is further provided in order to perform the process between the first press part 4 and the peeling part 6 at a temperature of the glass transition temperature ± 50 ° C. of the electrolyte membrane 10. You can also. As the high temperature holding means 8, for example, a sealed housing 81 is installed so as to seal the space from the first hot press section 4 to the peeling section 6, and a heating means 82 is provided so that the inside of the sealed housing 81 is heated to a high temperature. Can be configured. The heating means 82 preferably heats the sealed housing 81 to about 200 ° C., more preferably about 100 to 180 ° C. As the heating means 82, for example, a hot air supply device that supplies hot air, an infrared heater, or the like can be used. By providing the high temperature holding means 8 in this way, the electrolyte membrane 10 is not cooled after the first hot press portion 4 or the second hot press portion 5, so that the electrolyte membrane is a cause of peeling failure. Separation between the catalyst layer 10 and the catalyst layer 112 can be prevented. When the high temperature holding means 8 is provided, the heating rolls 51a and 51b of the second hot press unit 5 may heat the electrolyte membrane 10 and the catalyst layer transfer sheet 11, or simply apply without heating. You may just press. Also, the peeling rollers 61a and 61b may heat the electrolyte membrane 10 and the catalyst layer transfer sheet 11, or may not be heated.

  Moreover, in the said embodiment, although the manufactured membrane catalyst layer assembly 12 was demonstrated as the manufacturing apparatus 1 of the membrane catalyst layer assembly which winds up with the membrane catalyst layer assembly winding roll 22, as shown in FIG. After manufacturing the membrane catalyst layer assembly 12, the gas diffusion layer 13 is pressure-bonded to the upper surface and the lower surface of the membrane catalyst layer assembly 12 to manufacture the membrane electrode assembly 14, and the membrane electrode assembly winding roll 22 ′ is used. It can also be set as the manufacturing apparatus 1 'of a membrane electrode assembly which winds up. In this case, a gas diffusion layer supply unit 9 is installed between the peeling unit 6 and the cooling unit 7. The gas diffusion layer supply unit 9 includes gas diffusion layer supply rolls 91 a and 91 b in which a roll-shaped gas diffusion layer 13 is set, and the gas diffusion layer 13 is provided on each of the upper surface and the lower surface of the membrane catalyst layer assembly 12. Transport. Then, the membrane / catalyst layer assembly 12 and the gas diffusion layer 13 are sandwiched between the crimping rolls 15a and 15b, and the gas diffusion layer 13 is crimped to the upper and lower surfaces of the membrane / catalyst layer assembly 12 to manufacture the membrane / electrode assembly 14. To do. The pressure applied to the membrane catalyst layer assembly 12 and the gas diffusion layer 13 by the pressure rolls 15a and 15b is preferably 0.1 to 10 MPa, and the surface temperature of the pressure rolls 15a and 15b at that time is 30 to 200. It is preferable to set it as ° C. The completed membrane electrode assembly 14 is cooled by the cooling rolls 71a and 71b and taken up by the membrane electrode assembly winding roll 22 '. In addition, the material of the gas diffusion layer 13 is publicly known, and various gas diffusion layers constituting the fuel electrode and the air electrode can be used. In order to efficiently supply the fuel gas and the oxidant gas as fuel to the catalyst layer, It consists of a porous conductive substrate. Examples of the porous conductive substrate include carbon paper and carbon cloth.

  Further, as a post-process of the above-described membrane electrode assembly manufacturing apparatus 1 ′, a cutting section for cutting the completed membrane electrode assembly 14 to a desired size, or a gasket for installing a gasket on the cut membrane electrode assembly You may provide the installation part and the separator installation part which installs a separator so that the membrane electrode assembly 14 may be clamped from an upper surface and a lower surface.

  Moreover, in the said embodiment, the 2nd hot press part 5 can also be abbreviate | omitted.

  In the above embodiment, the catalyst layer 112 and the gas diffusion layer 13 are formed on both surfaces of the electrolyte membrane 10. However, the catalyst layer 112 and the gas diffusion layer 13 may be formed only on the upper surface or the lower surface of the electrolyte membrane 10. it can.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus of membrane catalyst layer assembly 2 Electrolyte membrane conveyance part 3 Catalyst layer transfer sheet conveyance part 4 1st heat press part (heat press part)
5 Second heat press section (pressurizing means)
6 Peeling unit 7 Cooling unit 8 High temperature holding means 10 Electrolyte membrane 11 Catalyst layer transfer sheet 111 Base material sheet 112 Catalyst layer 12 Membrane catalyst layer assembly 13 Gas diffusion layer 14 Membrane electrode assembly

Claims (18)

A method for producing a membrane-catalyst layer assembly in which a catalyst layer is formed on at least one surface of an electrolyte membrane,
A step of conveying a long electrolyte membrane;
A step of conveying a long catalyst layer transfer sheet having a catalyst layer formed on a base sheet in the same direction as the electrolyte membrane on at least one surface of the electrolyte membrane;
Pressurizing the catalyst layer transfer sheet while heating so that the catalyst layer is transferred to the electrolyte membrane; and
After the catalyst layer is transferred to the electrolyte membrane, the step of peeling the substrate sheet while heating the electrolyte membrane and the catalyst layer transfer sheet;
A process for producing a membrane catalyst layer assembly comprising:   The method for producing a membrane / catalyst layer assembly according to claim 1, wherein the peeling step peels the base sheet while heating the electrolyte membrane and the catalyst layer transfer sheet with a peeling roll.   The method for producing a membrane / catalyst layer assembly according to claim 1 or 2, wherein the steps from the heating and pressing step to the peeling step are performed at a temperature of glass transition temperature of the electrolyte membrane ± 50 ° C.   The production of a membrane / catalyst layer assembly according to any one of claims 1 to 3, further comprising a step of pressing the catalyst layer transfer sheet against the electrolyte membrane between the heating and pressing step and the peeling step. Method.   The method for producing a membrane / catalyst layer assembly according to claim 4, wherein the pressing step is performed while heating the catalyst layer transfer sheet.   The manufacturing method of the membrane catalyst layer assembly according to any one of claims 1 to 5, further comprising a step of cooling the membrane catalyst layer assembly after the peeling step.   The method for producing a membrane / catalyst layer assembly according to any one of claims 1 to 6, wherein, in the peeling step, the direction in which the base sheet is peeled forms an angle of 150 to 180 degrees with the transport direction of the electrolyte membrane. A method for producing a membrane catalyst layer assembly according to any one of claims 1 to 7,
Bonding a gas diffusion layer on the catalyst layer of the membrane catalyst layer assembly;
The manufacturing method of the membrane electrode assembly containing this. An apparatus for manufacturing a membrane catalyst layer assembly in which a catalyst layer is formed on at least one surface of an electrolyte membrane,
An electrolyte membrane transport section for transporting a long electrolyte membrane;
A catalyst layer transfer sheet transport unit for transporting a long catalyst layer transfer sheet having a catalyst layer formed on a base sheet in the same direction as the electrolyte membrane on the electrolyte membrane;
A hot press section that pressurizes the electrolyte membrane while heating the catalyst layer transfer sheet;
A peeling part installed downstream of the hot press part and peeling the substrate sheet while heating the electrolyte membrane and the catalyst layer transfer sheet;
An apparatus for producing a membrane / catalyst layer assembly comprising:   The membrane catalyst according to claim 9, wherein the peeling section is a pair of peeling rolls installed so as to sandwich the electrolyte membrane and the catalyst layer transfer sheet, and the peeling roll heats the electrolyte membrane and the catalyst layer transfer sheet. Layer assembly manufacturing equipment.   The apparatus for producing a membrane / catalyst layer assembly according to claim 9 or 10, further comprising a high-temperature holding means for maintaining a temperature from the hot press portion to the peeling portion at a glass transition temperature ± 50 ° C of the electrolyte membrane.   The high temperature holding means includes a hermetically sealed housing that seals a space from the hot press part to a peeling part, and a heating means that sets the temperature in the hermetic housing to a glass transition temperature ± 50 ° C of the electrolyte membrane. An apparatus for producing a membrane / catalyst layer assembly according to claim 1.   The membrane-catalyst layer assembly according to any one of claims 9 to 12, further comprising a pressurizing unit that is installed between the hot press part and the peeling part and pressurizes the catalyst layer transfer sheet against the electrolyte membrane. Manufacturing equipment.   The apparatus for producing a membrane / catalyst layer assembly according to claim 13, wherein the pressurizing unit heats the catalyst layer transfer sheet.   The said heat press part is a manufacturing apparatus of the membrane catalyst layer assembly in any one of Claims 9-14 which is a heating roll installed so that an electrolyte membrane and a catalyst layer transfer sheet may be pinched | interposed.   The apparatus for manufacturing a membrane catalyst layer assembly according to any one of claims 9 to 15, further comprising a cooling unit that is installed downstream of the peeling unit and cools the membrane catalyst layer assembly.   The said peeling part manufactures the membrane catalyst layer assembly in any one of Claims 9-16 which guides the direction which the base material sheet peels to make the angle of 150-180 degree | times with the conveyance direction of the said electrolyte membrane. Method. An apparatus for producing a membrane catalyst layer assembly according to any one of claims 1 to 17,
Gas diffusion layer bonding means installed downstream of the peeling portion and bonding the gas diffusion layer on the catalyst layer;
An apparatus for manufacturing a membrane electrode assembly, comprising:

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