JP2017037759A - Method for producing electrode sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an electrode sheet that is formed in manufacturing an MEA, in which the deformation of a catalyst layer due to heat treatment can be suppressed.SOLUTION: The present invention relates to a method for producing an electrode sheet 40 which is used for an MEA 11 and in which a catalyst layer 20 containing an electrolyte is formed on a sheet member 30. In the method, the catalyst layer is applied on the sheet member to form the electrode sheet, the electrode sheet is heated and then cooled in the ambient atmosphere, the electrode sheet being cooled in a restricted state at least during cooling.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing an electrode sheet.

  Nowadays, sales of automobiles equipped with fuel cells have begun. Since fuel cells do not emit greenhouse gases such as carbon dioxide and nitrogen oxides, they have less environmental impact, and further research and development are expected in the future. A fuel cell generates power by supplying an anode gas and a cathode gas to a membrane electrode assembly (hereinafter referred to as MEA) in which a catalyst layer on the anode side and the cathode side is provided on an electrolyte membrane and reacting them.

  For example, the MEA can be manufactured by forming a catalyst layer on a transfer sheet, drying and heat-treating the transfer sheet, and transferring the transfer sheet to a proton exchange membrane (see Patent Document 1). In Patent Document 1, heat treatment is performed before joining the catalyst layer and the proton exchange membrane, and heating and pressurization are performed at a temperature lower than the heat treatment.

JP 2004-288391 A

  The catalyst layer applied to the transfer sheet is cooled to room temperature after the heat treatment. Even if heat treatment, heating, and pressurization are performed as in the method according to Patent Document 1, warpage may occur in the catalyst layer and the transfer sheet due to thermal effects during the cooling. When the catalyst layer is warped as described above, there is a problem that it becomes difficult to recognize, for example, a corner portion when aligning the anode and the cathode with the electrolyte membrane, and the positioning work takes time.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for manufacturing an electrode sheet formed when manufacturing an MEA, which can suppress deformation of the catalyst layer due to heat treatment. .

  The present invention that achieves the above object is a method for producing an electrode sheet that is used in a membrane electrode assembly and has a catalyst layer containing an electrolyte formed on a sheet member, the catalyst layer being applied to the sheet member and the electrode A sheet is formed, the electrode sheet is heated, and then cooled in an air atmosphere, and the electrode sheet is cooled in a state of being restrained at least during the cooling.

  The electrode sheet manufacturing method according to the present invention is configured to cool the electrode sheet in a restrained state at least when the electrode sheet is cooled after heating as described above. Moisture contained in the catalyst layer is volatilized by heating, and the catalyst layer may warp due to moisture absorption during cooling in the air atmosphere. With respect to this, at least when the sheet member is cooled, the sheet member is cooled in a restrained state, thereby suppressing the deformation of the catalyst layer formed on the sheet member and smoothly performing the positioning operation of the anode and the cathode to the electrolyte membrane. Can do.

It is a flowchart which shows the manufacturing method of MEA which concerns on one Embodiment of this invention. It is sectional drawing shown about the principal part of the fuel cell using MEA. 3A is a view for explaining an application portion for applying a catalyst ink to a sheet member, FIG. 3B is a view for explaining a heat treatment portion for performing heat treatment on the catalyst ink, and FIG. 3C is a dried catalyst. It is a figure explaining the laminated part which laminates | stacks a layer on an electrolyte membrane. 4 (A) to 4 (C) are a perspective view and a front view showing a restraint portion used when cooling the catalyst layer applied to the sheet member, which is used in the MEA manufacturing method according to Embodiment 1 of the present invention. It is a figure and a top view. 5A and 5B are a perspective view and a front view showing a restraint portion according to a modification of the first embodiment, and FIGS. 5C and 5D are views of the restraint portion according to the modification. It is the perspective view and bottom view which looked up at a part from the lower side. 6 (A) to 6 (C) are a perspective view, a side view, a plan view, and FIG. 6 showing a main part of an apparatus used for cooling the catalyst layer applied to the sheet member in Embodiment 2 of the present invention. (D) is sectional drawing which follows the 6D-6D line | wire of FIG.6 (C). 7 (A) and 7 (B) are a perspective view and a side view showing the main part of the apparatus used when cooling the catalyst layer applied to the sheet member in Embodiment 3 of the present invention. 8 (A) to 8 (D) are a perspective view and a side view showing the main part of the apparatus used when cooling the catalyst layer applied to the sheet member in Embodiment 4 of the present invention. 9 (A) to 9 (C) are a perspective view, a side view, a plan view, and FIG. 9 showing a main part of an apparatus used for cooling the catalyst layer applied to the sheet member in Embodiment 5 of the present invention. (D) is a front view which shows the clamping part in Embodiment 5. FIG. 10 (A) and 10 (B) are a perspective view, a plan view, and FIG. 10 (C) showing an essential part of an apparatus used for cooling the catalyst layer applied to the sheet member in Embodiment 6 of the present invention. These are front views which show the clamping part in Embodiment 6. FIG. FIG. 11A to FIG. 11C are a perspective view, a plan view, and a side view showing the main part of the apparatus used when cooling the catalyst layer applied to the sheet member in Embodiment 7 of the present invention. It is a table | surface which shows the shape after a cooling, the deformation amount, etc. of the catalyst layer concerning the Example and comparative example of this invention.

(Embodiment 1)
Embodiments according to the present invention will be described below with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. The sizes and ratios of the members in the drawings are exaggerated for convenience of explanation and may be different from the actual sizes and ratios.

  FIG. 1 is a flowchart showing a MEA manufacturing method according to Embodiment 1 of the present invention. An outline of a method for manufacturing an MEA including a fuel cell according to the present embodiment will be described with reference to FIG. 1. The electrode layer 40 is formed by applying the catalyst layer 20 included in the anode 11b or the cathode 11c to the sheet member 30; The electrode sheet 40 is heated and then cooled in an air atmosphere. The electrode sheet 40 is cooled in a restrained state at least during cooling. Details will be described below.

(MEA)
FIG. 2 is a cross-sectional view showing a main part of a fuel cell using MEA. The MEA manufactured by the manufacturing method according to the present embodiment is a constituent element of the fuel cell 10 used when energy is generated by an electrochemical reaction in the fuel cell. First, the MEA will be described below.

  The MEA 11 generates electric power by chemically reacting the supplied oxygen and hydrogen. As shown in FIG. 2, the MEA 11 is formed by joining the anode 11b to one side of the electrolyte membrane 11a and joining the cathode 11c to the other side. The electrolyte membrane 11a is made of, for example, a solid polymer material and is formed in a thin plate shape.

  As the solid polymer material, for example, a fluorine-based resin that conducts hydrogen ions and has good electrical conductivity in a wet state is used. The anode 11b is formed by laminating a catalyst layer 20, a water repellent layer, and a gas diffusion layer, and is formed in a thin plate shape slightly smaller than the electrolyte membrane 11a. The cathode 11c is formed by laminating a catalyst layer 20, a water repellent layer, and a gas diffusion layer, and is formed in a thin plate shape with the same size as the anode 11b.

  The catalyst layer 20 of the anode 11b and the cathode 11c is obtained by drying and heat-treating a so-called catalyst ink in which an ionomer and catalyst particles are contained in a solvent.

  Examples of the solvent include tap water, pure water, ion exchange water, distilled water, and the like, cyclohexanol, methanol, ethanol, n-propanol (n-propyl alcohol), isopropanol (IPA), n-butanol, sec-butanol. , Isobutanol, tert-butanol and other lower alcohols having 1 to 4 carbon atoms, propylene glycol, benzene, toluene, xylene and the like, but are not limited thereto. Besides these, butyl acetate alcohol, dimethyl ether, ethylene glycol, and the like may be used as a solvent. These solvents may be used alone or in the form of a mixture of two or more.

  Examples of the ionomer include, but are not limited to, a fluorine-based polymer electrolyte material and a hydrocarbon-based polymer electrolyte material. Examples of the fluoropolymer electrolyte material include perfluorocarbon sulfonic acid polymers such as Nafion (registered trademark), Aciplex (registered trademark), and Flemion (registered trademark), perfluorocarbon phosphonic acid polymers, and trifluorostyrene sulfonic acid. Examples thereof include an ethylene-based polymer, an ethylenetetrafluoroethylene-g-styrenesulfonic acid-based polymer, an ethylene-tetrafluoroethylene copolymer, and a polyvinylidene fluoride-perfluorocarbonsulfonic acid-based polymer. Examples of the hydrocarbon-based polymer electrolyte material include sulfonated polyethersulfone (S-PES), sulfonated polyaryletherketone, sulfonated polybenzimidazole alkyl, phosphonated polybenzimidazole alkyl, sulfonated polystyrene, and sulfonated. Examples include polyetheretherketone (SPEEK) and sulfonated polyphenylene (S-PP).

  The catalyst particles include at least a substance having a catalytic action, and include, for example, a catalytic metal having a catalytic action and a catalyst carrier that supports the catalytic metal.

  The catalyst metal is, for example, a platinum-containing catalyst metal, but is not limited thereto. Examples of the platinum-containing catalyst metal include platinum (Pt) simple particles, or platinum particles and ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), osmium (Os), tungsten (W). Lead (Pb), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), vanadium (V), molybdenum (Mo), gallium (Ga) and aluminum (Al) A mixture with at least one other metal particle selected from the group consisting of, an alloy of platinum and another metal, and the like can be mentioned.

  The catalyst carrier has, for example, electronic conductivity, and the main component is carbon. Examples of the catalyst carrier include, but are not limited to, carbon particles made of carbon black (Ketjen black, oil furnace black, channel black, lamp black, thermal black, acetylene black, etc.), activated carbon, and the like.

  The gas diffusion layers of the anode 11b and the cathode 11c are formed of, for example, carbon cloth, carbon paper, or carbon felt woven with yarns made of carbon fibers having sufficient gas diffusibility and conductivity.

  Although not a constituent element of the MEA 11, the separators 13 and 14, as shown in FIG. 2, energize the electric power generated in the MEA 11 while isolating the adjacent MEAs 11 in the stacked fuel cells 10.

(MEA production equipment)
Next, an MEA manufacturing apparatus will be described. 3A is a view for explaining an application portion for applying a catalyst ink to a sheet member, FIG. 3B is a view for explaining a heat treatment portion for performing heat treatment on the catalyst ink, and FIG. 3C is a dried catalyst. It is a figure explaining the laminated part which laminates | stacks a layer on an electrolyte membrane. 4A to 4C are a perspective view and a front view showing a restraining portion used when cooling the catalyst ink applied to the sheet member, which is used in the MEA manufacturing method according to Embodiment 1 of the present invention. It is a figure and a top view.

  The MEA manufacturing apparatus according to this embodiment will be briefly described with reference to FIGS. 3 to 4. An application unit 110 that applies a catalyst layer, which is a material of MEA, to the sheet member 30 in the state of the catalyst ink 20, and the sheet member 30 and a heat treatment part 120 for drying and heat-treating the catalyst ink 20, a restraint part 130 for restraining the sheet member 30 coated with the catalyst ink 20, and a cooling part (not shown) for cooling the heat-treated catalyst layer 20. A laminated portion 140 for laminating the dried catalyst layer 20 on the electrolyte membrane 11a.

  In the first embodiment, the sheet member 30 to which the catalyst ink 20 is temporarily applied is configured as a so-called sheet-like sheet member in which the catalyst ink 20 is applied alone to one sheet member 30. Details will be described below.

(Applying part)
The application unit 110 includes an applicator 111 that can adjust the ink supply pressure, as shown in FIG. The catalyst ink 20 discharged from the applicator 111 is applied to a sheet member 30 configured as a transfer sheet containing a material such as PTFE. As long as the catalyst ink 20 can be applied to the sheet member 30, the configuration for applying the catalyst ink 20 is not limited to the applicator.

  The adjustment of the catalyst ink before applying the catalyst ink 20 to the sheet member 30 is the same as that conventionally known, and thus the description thereof is omitted.

(Heat treatment part)
The heat treatment section 120 includes a heater 121 capable of adjusting the temperature as shown in FIG. The heat treatment in the present embodiment refers to a process such as heating, and the catalyst layer 20 is heated to a temperature higher than the glass transition temperature included in the catalyst layer 20 by the heat treatment, and the mechanical strength and the like are improved. Specific examples of the heater 121 include an electric heater, but the heater 121 is not limited to an electric heater as long as the heat treatment and drying of the catalyst ink 20 can be performed. At the time of drying, a part or all of the solvent component in the catalyst ink 20 is volatilized by using the heater 121 and drying is performed. Note that the heat treatment and the drying may be performed as separate treatments, or the heat treatment and the drying may be performed together in one treatment.

(Restraining part)
The restraining portion 130 is particularly used when the electrode sheet 40 including the catalyst layer 20 that has been dried and heat-treated is cooled. As shown in FIGS. 4A to 4C, the restraining unit 130 includes a table 131 on which a member that restrains the electrode sheet 40 is placed, a placement unit 132 on which the electrode sheet 40 is placed on the table 131, In the sheet member 30, a contact portion 133 that makes contact on the surface opposite to the surface on which the placement portion 132 contacts, a movable portion 134 that enables the contact portion 133 to move in the thickness direction of the electrode sheet 40, and a movable portion 134. And a support portion 135 that supports the. In the restraining part 130, the contact part 133, the movable part 134, and the support part 135 described above are configured in pairs as shown in FIGS. 4 (A) to 4 (C).

  The table 131 is configured to install the placement unit 132, the contact unit 133, the movable unit 134, and the support unit 135. The placement unit 132 is a flat plate-like portion installed on the table 131 and has a configuration for installing the electrode sheet 40. The support part 135 is a structure for movably supporting the movable part 134 and the contact part 133 for pressing the electrode sheet 40 from above.

  The movable portion 134 is configured to be vertically movable with respect to the support portion 135 in FIG. In other words, the movable part 134 is configured to be movable toward and away from the mounting part 132. In the present embodiment, the support unit 135 incorporates a motor (not shown) for moving the movable unit 134, but the configuration for moving the movable unit 134 is not limited to the motor as long as the movable unit 134 can be moved. . The contact portion 133 is provided at an end portion in the moving direction of the arm-shaped movable portion 134.

  In the present embodiment, the sheet member 30 is configured in a rectangular shape. The contact part 133 is formed in a flat plate shape, and is configured so as to sandwich the opposite side of the four sides of the sheet member 30, in the present embodiment, two opposite sides of the rectangular shape together with the placement unit 132. Yes.

  The contact portion 133 is configured to contact and press the outer portion of the sheet member 30 where the catalyst ink 20 is not applied.

(Laminated part)
As shown in FIG. 3C, the stacking unit 140 has a pair of rollers 141 and 142 that transfer the catalyst layer 20 applied to the sheet member 30 to the electrolyte membrane 11a and are held rotatably. The catalyst layer 20 applied to the sheet member 30 is transferred onto the electrolyte membrane 11a by the rollers 141 and 142 as shown in FIG. The structure in which the catalyst ink is applied to the electrolyte membrane is also called CCM (Catalyst Coated Membrane CCM).

  When the catalyst ink 20 is transferred to the electrolyte membrane 11a, the gas diffusion layer is attached to the electrolyte membrane 11a by a roller similar to the rollers 141 and 142. As a result, the MEA 11 is formed.

(Cooling section)
The cooling unit that cools the heat-treated catalyst layer 20 is configured by leaving the sheet member 30 coated with the catalyst ink 20 on the placement unit 132 in an air atmosphere for a predetermined time. However, the configuration of the cooling unit is not limited to the above, and may be configured by forcibly cooling using a blower or the like in the air atmosphere without increasing the ambient temperature.

(Method for producing MEA)
Next, in the MEA manufacturing method according to the present embodiment, a process from application of the catalyst ink to the sheet member to transfer to the electrolyte membrane will be described. The other steps are the same as those in the prior art, and will not be described.

  An outline of the MEA manufacturing method according to the present embodiment will be described with reference to FIG. 1. Application of the catalyst ink (step ST1), drying / heat treatment of the catalyst ink (step ST2), restraint and cooling of the electrode sheet (step) ST3) and release of constraint (step ST4).

  First, when the catalyst ink 20 is applied, the catalyst ink 20 prepared on the sheet member 30 is applied by the application unit 110 described above to form the electrode sheet 40 (step ST1). At the time of drying, for example, the catalyst ink 20 is dried by the heater 121 in a heat treatment furnace or the like, and after or simultaneously with the drying, heat treatment is performed at a temperature higher than the glass transition temperature of the electrolyte and lower than the decomposition temperature (step ST2). In the present embodiment, a configuration obtained by drying the catalyst ink 20 is referred to as a catalyst layer.

  After drying, the electrode sheet 40 is placed on the placement portion 132 of the restraining portion 130. Then, the movable portion 134 approaches the placement portion 132 on which the sheet member 30 is placed, and the electrode sheet 40 is sandwiched between the placement portion 132 and the contact portion 133. The electrode sheet 40 is cooled while being sandwiched between the placement portion 132 and the contact portion 133 in the air atmosphere (step ST3). When the cooling is finished, the movable part 134 is separated from the electrode sheet 40, the holding by the contact part 133 and the placing part 132 is released, and the restriction by the restricting part 130 is released (step ST4). Release by restraint is performed below the glass transition temperature of the electrolyte.

(Function and effect)
Next, the function and effect according to this embodiment will be described. In this embodiment, the electrode sheet 40 formed by applying the catalyst ink 20 is heated, and then cooled in the air atmosphere. The electrode sheet 40 is configured to cool at least in a state of being constrained flatly at the time of cooling. Moisture contained in the catalyst layer 20 is volatilized by heating, and the catalyst layer 20 may be warped due to moisture absorption during cooling in the air atmosphere.

  On the other hand, in the present embodiment, the electrode sheet 40 is restrained flatly by the restraining portion 130 at least during cooling, thereby preventing the catalyst layer 20 from warping, and to the electrolyte membrane 11a of the anode 11b and the cathode 11c. Can be accurately positioned.

  In addition, the restraining portion 130 is configured to restrain the electrode sheet 40 in the thickness direction. The warp generated in the catalyst layer 20 occurs particularly in the thickness direction of the catalyst layer 20. Therefore, it is possible to effectively prevent warping of the catalyst layer 20 by restraining the electrode sheet 40 in the thickness direction by the restraining portion 130.

  Further, the restraint in the thickness direction on the electrode sheet 40 can be achieved by causing the contact portion 133 to approach the placement portion 132 by the movable portion 134 and applying a load in the thickness direction of the electrode sheet 40. .

  Further, in the above, the outer side is configured to be sandwiched by the restraining portion 130 rather than the portion of the electrode sheet 40 where the catalyst layer 20 is provided. Therefore, even if the electrode sheet 40 is constrained by the constraining portion 130, no trace due to the confinement is formed in the resulting catalyst layer 20. Therefore, deformation such as warpage of the catalyst layer 20 can be prevented and the quality of the catalyst layer 20 can be improved.

  Moreover, the restraint part 130 can prevent the deformation | transformation by a curvature by pinching the edge | side which separated at least 2 or more in the rectangular-shaped electrode sheet 40 using the contact part 133 in this embodiment especially two sides which oppose.

  In addition, the restraining portion 130 suppresses deformation such as warpage of the sheet member 30 by holding the sheet member 30 configured in a sheet shape between the flat plate-like placement portion 132 and the pair of flat contact portions 133. be able to.

  Moreover, the heating with respect to the sheet | seat member 30 is more than the glass transition temperature of the electrolyte which comprises a catalyst layer, and is comprised below decomposition temperature. The present inventors have found that the warpage of the catalyst layer 20 is noticeable in cooling when the catalyst layer 20 is heated to the glass transition temperature or higher. Therefore, warping of the catalyst layer 20 can be effectively prevented by performing at least cooling in a state where the electrode sheet 40 is restrained when the catalyst layer 20 is heated to the glass transition temperature or higher. In addition, by setting the heating temperature of the electrode sheet 40 to be equal to or lower than the decomposition temperature of the electrolyte, it is possible to improve the cell performance when the fuel cell is formed while preventing the composition of the catalyst layer from changing.

  Further, the restraint of the electrode sheet 40 by the restraining portion 130 is released at a temperature equal to or lower than the glass transition temperature of the electrolyte constituting the catalyst layer 20. The deformation of the catalyst layer 20 can be noticeable when the catalyst layer 20 is heated to a high temperature such as the glass transition temperature or higher. Therefore, it is possible to prevent the catalyst layer 20 from being deformed after the restraint is released by releasing the restraint by the restraining portion 130 at a temperature equal to or lower than the glass transition temperature.

(Modification of Embodiment 1)
5A and 5B are a perspective view and a front view showing a restraint portion according to a modification of the first embodiment, and FIGS. 5C and 5D are views of the restraint portion according to the modification. It is the perspective view and bottom view which looked up at a part from the bottom. In the first embodiment, the embodiment in which the contact portion 133 is paired and abuts against two of the four sides of the sheet member 30 to sandwich the electrode sheet 40 together with the placement portion 132 has been described. However, in addition to the above, the following configuration can also be adopted.

  In this modified example, the restraining portion 130a includes the table 131, the placement portion 132, the movable portion 134, the support portion 135, and the outer periphery of the electrode sheet 40, as shown in FIGS. 5 (A) to 5 (D). And a contact portion 136 that holds the electrode sheet 40 together with the placement portion 132.

  In the modification of the first embodiment, the contact portion 133, the movable portion 134, and the support portion 135 are not configured as a pair, and in particular, the configuration of the contact portion 136 is different from the contact portion 133 of the first embodiment. . Since other configurations are the same as those of the first embodiment, description thereof is omitted.

  In the present modification, the contact portion 136 is in contact outside the portion where the catalyst layer 20 is disposed in the rectangular sheet member 30. As shown in FIGS. 5C and 5D, the contact portion 136 has a so-called frame shape in which a rectangular outer peripheral portion is a contact portion with the sheet member 30. Such a contact portion 136 can be moved by the movable portion 134, and the electrode sheet 40 can be sandwiched between the placement portion 132 and the contact portion 136.

  By sandwiching the electrode sheet 40 configured in this way using the frame-shaped contact portion 136 and the mounting portion 132, the sheet member 30 can be made more than when the contact portion 133 of the first embodiment is used. It can be firmly held. Therefore, it is possible to more effectively suppress deformation such as warpage that occurs during conventional cooling.

(Embodiment 2)
6 (A) to 6 (C) are a perspective view and a side view showing a main part of an apparatus used when cooling the catalyst layer applied to the sheet member in the MEA manufacturing method according to Embodiment 2 of the present invention. FIG. 6D is a cross-sectional view taken along line 6D-6D of FIG. 6C. In the first embodiment, the embodiment in which the sheet-like sheet member 30 to which the catalyst ink 20 is applied is sandwiched between the flat plate-like mounting portion 132 and the contact portion 133 has been described. However, in addition to the above, the following configuration can be adopted.

  In the electrode sheet 60 according to the second embodiment, as shown in FIG. 6A and the like, the catalyst layer 20 is disposed on a sheet member 50 configured in a long shape, not in a sheet shape. The electrode sheet manufacturing apparatus according to the second embodiment guides the electrode sheet 60 in the conveyance direction, as shown in FIGS. 6A to 6D, and a conveyance unit 210 that conveys the long electrode sheet 60. The rail member 220 for sandwiching the end portion in the transverse direction of the electrode sheet 60 and the holding portion 230 for holding the electrode sheet 60 so as not to contract in the transverse direction together with the rail member 220 are provided.

  Although not illustrated in FIGS. 6A to 6D, the electrode sheet manufacturing apparatus according to the second embodiment includes an application unit 110, a heat treatment unit 120, and a stacking unit 140 illustrated in FIG. 3. However, since it is the same as that of Embodiment 1, description is abbreviate | omitted. In addition, in the second and subsequent embodiments, when the long electrode sheet 60 is conveyed, the conveyance direction of the electrode sheet 60 is a conveyance direction X, and the transverse direction of the electrode sheet 60 intersecting the conveyance direction X is the transverse direction Y. Is written.

  The transport unit 210 is a so-called roller for moving the long electrode sheet 60 in the transport direction X. The transport unit 210 transports the electrode sheet 60 from upstream to downstream in the transport direction X while contacting a part of the electrode sheet 60 as shown in FIGS. In FIG. 6 (B), the electrode sheet 60 is conveyed diagonally to the left from the lower side, wound around the conveying unit 210, and conveyed rightward in the horizontal direction. However, if the electrode sheet 60 can be conveyed, the conveyance direction of the electrode sheet 60 is not limited to FIG. 5 (A) to FIG. 5 (C).

  In this embodiment, the rail member 220 extends in the longitudinal direction of the electrode sheet 60 and guides the conveyance of the electrode sheet 60. As shown in FIG. 6D, the rail member 220 is a pair of rod-like members disposed at both ends in the transverse direction Y of the electrode sheet 60. In FIG. 6C, the rail member 220 has a circular cross-sectional shape. However, the shape of the electrode sheet 60 may be, for example, a polygon other than that shown in FIG.

  As shown in FIG. 6B and the like, the holding unit 230 is provided in a plurality of places in the conveying direction X of the electrode sheet 60, and is provided at both ends in the transverse direction Y of the electrode sheet 60. The holding part 230 has a rotatable roller as shown in FIG. 6D and the like, and sandwiches each end part at both ends of the electrode sheet 60 together with the rail member 220.

  In FIG. 6D, the rotation axis C of the holding unit 230 is inclined with respect to the transverse direction Y. However, the contraction of the electrode sheet 60 is not limited to the case shown in FIG. May be parallel to the transverse direction Y. The cooling in the second embodiment is performed when the electrode sheet 60 passes through the rail member 220 and the holding unit 230.

  Thus, when the electrode sheet 60 is long, the catalyst layer constituting the electrode sheet 60 being cooled by sandwiching both ends of the electrode sheet 60 in the transverse direction Y intersecting the transport direction X Deformation such as 20 warpage can be suppressed. In the present embodiment, both ends of the electrode sheet 60 are wound around the rail member 220 as described above, and the electrode sheet 60 is transported while being sandwiched between the rail member 220 and the rollers constituting the holding unit 230, thereby causing warpage or the like. Deformation can be prevented.

(Embodiment 3)
FIGS. 7A and 7B are a perspective view and a side view showing a main part of an apparatus used for cooling the catalyst layer applied to the sheet member in the MEA manufacturing method according to Embodiment 3 of the present invention. It is. Although Embodiment 2 demonstrated embodiment which clamps the both ends of the elongate electrode sheet 60 with the rail member 220 and the holding | maintenance part 230, the following structures other than the above are employable.

  As shown in FIGS. 7A and 7B, the electrode sheet manufacturing apparatus according to the third embodiment includes a transport unit 310 for transporting the long electrode sheet 60 and a transport unit 310. And a rotating part 320 that sandwiches the electrode sheet 60 being conveyed by one member. Although not shown in FIGS. 7A and 7B, the electrode sheet manufacturing apparatus according to the third embodiment includes an application unit 110, a heat treatment unit 120, a stacking unit 140, and a stacking unit 140 illustrated in FIG. However, since it is the same as that of the first embodiment, the description thereof is omitted.

  The transport unit 310 has a roller shape as shown in FIG. 7A and the like, contacts a part of the long electrode sheet 60 sent from the upstream, and transports the electrode sheet 60 downstream by rotation. As shown in FIG. 7A, contact portions 311 and 312 that come into contact with the electrode sheet 60 are provided at both ends in the transverse direction Y of the transport portion 310, and the other portions are the portions of the catalyst ink 20. It is configured not to touch.

  As shown in FIG. 7A and the like, the rotating unit 320 is in contact with the electrode sheet 60 and transports the electrode sheet 60 by movement, and a pair of holding units 322 that hold the belt 321 movably. And a roller (not shown) configured to rotate and move the belt 321 by rotation.

  The belt 321 is configured to be movable by a roller (not shown) included in the rotating unit 320. The belt 321 contacts the electrode sheet 60 on the side where the catalyst layer 20 is not applied, and moves the electrode sheet 60 downstream by moving in synchronization with the rotation of the transport unit 310 by the roller. The holding unit 322 holds the belt 321 so as to be movable, and holds a roller (not shown) so as to be rotatable.

  The rotating unit 320 has a built-in device for circulating the cooling water as a configuration for cooling. By configuring the rotation unit 320 in this way, the electrode sheet 60 is cooled when passing through the rotation unit 320. When the electrode sheet 60 is conveyed, the electrode sheet 60 is sandwiched by using the contact portions 311 and 312 constituting the roller-shaped conveyance unit 310 and the belt 321, thereby warping the catalyst layer 20 as in the above embodiment. Can be suppressed.

(Embodiment 4)
FIGS. 8A and 8B are perspective views showing essential parts of an apparatus used when cooling the catalyst ink (catalyst layer) applied to the sheet member in the MEA manufacturing method according to Embodiment 4 of the present invention. It is a figure and a side view. In the first embodiment, the two sides of the sheet-like electrode sheet 40 are sandwiched, and in the second and third embodiments, the both ends in the transverse direction Y of the long electrode sheet 60 are sandwiched. However, in addition to the above, the following configuration can be adopted.

  The electrode sheet manufacturing apparatus according to the fourth embodiment includes a roller 410 that feeds out the sheet member 50, a roller 420 that winds up the sheet member 50, and an electrode sheet 60 as shown in FIGS. 8 (A) and 8 (B). There are clamping portions 430 and 440 that are in contact with each other and clamp the electrode sheet 60 together. Although not shown in FIGS. 8A and 8B, the electrode sheet manufacturing apparatus according to the fourth embodiment includes a coating unit 110, a heat treatment unit 120, and a stacking unit 140 illustrated in FIG. However, since it is the same as that of Embodiment 1, description is abbreviate | omitted.

  The roller 410 is a roller on the side of feeding the long sheet member 50, and the roller 420 is a roller on the side of winding up the sheet member 50 supplied from the roller 410. As shown in FIG. 8 (B), the sandwiching portion 430 is disposed between the roller 410 and the roller 420, partially contacts the elongated electrode sheet 60, and moves the electrode sheet 60. A plurality of rollers 432 for moving the belt 431 by rotation. The sandwiching portion 430 is disposed on one surface side of the electrode sheet 60 and is disposed below the electrode sheet 60 in FIG. 8A and 8B, the application part and the heat treatment part are not shown, but they are arranged from the roller 410 to the sandwiching parts 430 and 440.

  The belt 431 is an endless belt, and sandwiches the electrode sheet 60 together with the sandwiching portion 440 and conveys it downstream. The rollers 432 are configured to rotate the belt 431, and 14 rollers are provided in FIG. 8B. However, the number and arrangement of the rollers are not limited to the above as long as the belt 431 can be rotated.

  As shown in FIG. 8B, the sandwiching portion 440 is disposed on the surface opposite to the sandwiching portion 430 with respect to the electrode sheet 60. The clamping unit 440 includes a belt 441 that moves the electrode sheet 60 together with the belt 431 of the clamping unit 430, a roller 442 that moves the belt 441 by rotation, and an electrode sheet that is provided on the belt 441 and includes the catalyst ink 20 at least during cooling. And a pressing portion 443 for clamping 60.

  The belt 441 is the same as the belt 431 in the clamping unit 430, and the roller 442 is the same as the roller 432 of the clamping unit 430, and thus description thereof is omitted. The pressing portion 443 has a frame shape provided on the belt 441. The pressing portion 443 is configured in a shape similar to the shape of the contact portion 136 in FIG. A plurality of pressing portions 443 are arranged on the belt 441, and come into contact with the sheet member 50 outside the catalyst layer 20 by adjusting the feeding speeds of the belts 431 and 441 to restrain the electrode sheet 60.

  In the apparatus having the above-described configuration, the sheet member 50 is sent out from the roller 410, the catalyst ink 20 is supplied by the coating unit 110, the heat treatment is performed by the heat treatment unit 120, and the cooling is performed in an air atmosphere. When cooling, the electrode sheet 60 is conveyed while being clamped by the pressing portion 443 of the clamping unit 440 and the belt 431 of the clamping unit 430. By comprising in this way, deformation | transformation, such as curvature of the catalyst layer 20 which comprises the elongate electrode sheet 60 similarly to Embodiment 2, 3, can be suppressed. In the above description, the pressing portion 443 is provided only in the holding portion 440. However, the holding portion 430 may be provided in the same manner, or may be provided in both the holding portions 430 and 440.

(Embodiment 5)
9 (A) to 9 (C) are a perspective view, a side view, and a side view showing a main part of an apparatus used when cooling the catalyst ink (catalyst layer) applied to the sheet member in Embodiment 5 of the present invention. FIG. 9D is a front view showing the holding portion in the fifth embodiment. Embodiment 2 demonstrated embodiment which clamps the both ends in the cross direction Y of the elongate electrode sheet 60 with the rail member 220 and the holding | maintenance part 230. As shown in FIG. However, in addition to the above, the following configuration may be employed.

  As shown in FIGS. 9A to 9D, the electrode sheet manufacturing apparatus according to Embodiment 5 includes a roller 510 that feeds out the sheet member 50, a roller 520 that winds up the sheet member 50, a roller 510, and A belt 530 provided between the rollers 520 and conveying the sheet member 50 from the rollers 510 to the rollers 520, a plurality of rollers 540 provided in contact with the inside of the belt 530 and moving the belt 530 by rotation; And a sandwiching portion 550 that sandwiches each end portion of the sheet member 50 in the transverse direction Y.

  Although not shown in FIGS. 9A to 9D, the electrode sheet manufacturing apparatus according to the second embodiment includes the coating unit 110, the heat treatment unit 120, and the stacking unit 140 illustrated in FIG. However, since it is the same as that of Embodiment 1, description is abbreviate | omitted. The rollers 510 and 520 are the same as the rollers 410 and 420 of the fourth embodiment, the belt 530 is the same as the belt 431 of the fourth embodiment, and the roller 540 is the same as the roller 432 of the fourth embodiment. Is omitted.

  As shown in FIG. 9D, the sandwiching unit 550 is configured to be rotatable, and the rotating units 551 and 552 that move the sheet member 50 to the roller 520 while being in contact with the sheet member 50, and the rotating units 551 and 552. And a support portion 553 that rotatably supports the.

  The sandwiching portions 550 are arranged in pairs on the sides of the belt 530. The support portion 553 is configured to include a shaft that rotates the rotating portions 551 and 552. Although the structure of the motor etc. which rotate the rotation parts 551 and 552 in the support part 553 is comprised, it may comprise separately in the vicinity of the support part 5553.

  The rotating parts 551 and 552 are roller-shaped members having a circular cross section. The rotating portion 551 contacts the sheet member 50 disposed on the upper portion of the belt 530, and the rotating portion 552 contacts the belt 530. The rotating portions 551 and 552 are arranged obliquely, not perpendicularly or parallel to the conveying direction X of the sheet member 50 in the plan view shown in FIG. 9C. The rotating parts 551 and 552 are configured to be arranged outward as they go downstream in the transport direction X, as shown in FIG.

  With this configuration, when the electrode sheet 60 is conveyed from the roller 510 to the roller 520, the rotating units 551 and 552 of the clamping unit 550 rotate with the movement of the electrode sheet 60 and the belt 530. Since the rotating parts 551 and 552 are arranged to be inclined with respect to the transport direction X, not only the sheet member 50 is transported in the transport direction X, but also the tension that pulls the electrode sheet 60 outward in the transverse direction Y. Cause it to occur. Therefore, even if the electrode sheet 60 is subjected to heat treatment or cooling during conveyance as in the above embodiment, the catalyst layer 20 can be prevented from contracting and deformation such as warpage can be suppressed.

(Embodiment 6)
FIGS. 10A and 10B are a perspective view, a plan view, and a plan view showing an essential part of an apparatus used for cooling the catalyst ink (catalyst layer) applied to the sheet member in Embodiment 6 of the present invention. FIG. 10C is a front view showing the clamping portion in the sixth embodiment. In the fifth embodiment, the embodiment has been described in which the rotating units 551 and 552 constituting the clamping unit 550 are arranged obliquely with respect to the conveyance direction X of the sheet member 50. However, it is possible to adopt the following configuration.

  The electrode sheet manufacturing apparatus according to the present embodiment will be outlined with reference to FIGS. 10A to 10C. A roller 610 that feeds out the sheet member 50, a roller 620 that winds up the sheet member 50, and a roller 610 and a roller 620, a belt (not shown) that conveys the sheet member 50 from the roller 610 to the roller 620, and a roller that is in contact with the inside of the belt and rotates the belt by rotation ( (Not shown), a plurality of clamping units 630 that clamp end portions in the transverse direction Y intersecting the conveyance direction X of the sheet member 50, and a moving unit 640 that moves the plurality of clamping units 630 in accordance with the conveyance of the sheet member 50. , 650.

  Although not illustrated in FIGS. 10A to 10C, the electrode sheet manufacturing apparatus according to the sixth embodiment includes an application unit 110, a heat treatment unit 120, and a stacking unit 140 illustrated in FIG. 3. However, since it is the same as that of Embodiment 1, description is abbreviate | omitted. The rollers 610 and 620 are the same as the rollers 510 and 520 of the fifth embodiment, and a belt (not shown) disposed between the roller 610 and the roller 620 and a roller (not shown) for operating the belt are the same as those of the fifth embodiment. Since it is the same as that of the belt 530 and the roller 540, the description is omitted.

  As shown in FIG. 10C, the sandwiching portion 630 includes a moving portion 640 or an attaching portion 631 attached to the moving portion 650, a fixing portion 632 that contacts one side of the sheet member 50, and a fixing portion 632 in the sheet member 50. Has a movable portion 633 that contacts the opposite surface and is movable toward and away from the fixed portion 632.

  The attachment part 631 is formed in a U-shape, for example, and is attached to the moving parts 640 and 650 so that the holding part 630 can be moved. However, as long as it can be attached to the moving parts 640 and 650, the shape of the attachment part is not limited to the U-shape. The fixed portion 632 is formed in an L shape, the horizontal portion forms a contact portion with the sheet member 50, and the vertical portion forms a mounting portion of the movable portion 633. The movable portion 633 is attached to a vertical portion of the fixed portion 632 and is configured to be able to approach and separate from the fixed portion 632.

  The moving unit 640 includes a belt 641 formed in a closed shape when viewed in plan in FIG. 10B, and rollers 642 and 643 that rotate the belt 641. The belt 641 is configured in an endless shape, and a holding portion 630 is attached to the upper portion. The rollers 642 and 643 are configured to rotate the endless belt 641, the roller 642 is arranged on the upstream side in the transport direction X (below in FIG. 10B), and the roller 643 is downstream in the transport direction X (Above FIG. 10B). As shown in FIG. 10B, the roller 642 disposed on the upstream side is disposed closer to the electrode sheet 60 in the transverse direction Y than the roller 643 disposed on the downstream side.

  The moving unit 650 includes a belt 651 and rollers 652 and 653. The belt 651 is disposed symmetrically with the belt 641 as shown in FIG. 10B, and the other points are the same as the belt 641, and thus description thereof is omitted. Since the rollers 652 and 653 are the same as the rollers 642 and 643, description thereof is omitted.

  With this configuration, when the plurality of sandwiching portions 630 sandwich the sheet member 50, the moving portions 640 and 650 are separated from the sheet member 50 in the transverse direction Y. When the sheet member 50 sandwiched by the sandwiching unit 630 is conveyed downstream, the sandwiching unit 630 is separated from the sheet member 50 in the transverse direction Y, whereby the electrode sheet 60 is further pulled in the transverse direction Y. Therefore, the electrode sheet 60 is tensioned in the transverse direction Y by the sandwiching portion 630. Therefore, it can suppress that the catalyst layer 20 of the electrode sheet 60 generate | occur | produces the curvature etc. in the case of cooling similarly to the said embodiment.

(Embodiment 7)
11 (A) to 11 (C) are a perspective view, a plan view, and a side view showing an essential part of an apparatus used for cooling the catalyst ink (catalyst layer) applied to the sheet member in Embodiment 7 of the present invention. FIG. Although Embodiment 1-6 demonstrated embodiment which clamps the electrode sheet 40 or the electrode sheet 60 from the direction which cross | intersects the surface of the electrode sheet 40 or the electrode sheet 60, the following structures are also employable. .

  As shown in FIGS. 11A to 11C, the electrode sheet manufacturing apparatus according to the seventh embodiment includes a roller 710 that sends out the sheet member 50, a roller 720 that winds up the sheet member 50, and a roller 710. A belt 730 disposed between the rollers 720 and partially contacting the elongated sheet member 50 to move the sheet member 50 in the conveying direction X, a roller 740 for operating the belt 730, and the sheet member 50 being the belt 730. A suction mechanism 750 that sucks the electrode sheet 60 onto the belt 730 while passing through the top.

  Although not shown in FIGS. 11A to 11C, the electrode sheet manufacturing apparatus according to the seventh embodiment includes an application unit 110, a heat treatment unit 120, and a stacking unit 140 illustrated in FIG. 3. However, since it is the same as that of Embodiment 1, description is abbreviate | omitted. Moreover, since the rollers 710 and 720 are the same as the rollers 510 and 520 of the fifth embodiment, and the roller 740 is the same as the roller 540 of the fifth embodiment, description thereof is omitted.

  As shown in FIGS. 11A and 11B, the belt 730 has numerous small holes on its surface so that the electrode sheet 60 can be sucked into the belt 730 by operating the suction mechanism 750. The small holes are indicated by broken lines in FIGS. 11A and 11B, are configured in a circular shape, and are regularly arranged in the transverse direction and the conveying direction. However, the shape and arrangement of the small holes are not limited to the above as long as the electrode sheet 60 can be sucked.

  The suction mechanism 750 generates a suction force for attracting the sheet member 50 to the belt 730. The suction mechanism 750 includes a housing that forms a space for generating a suction force so as to be isolated from the outside, as shown in FIG.

  The housing is configured to include openings that communicate with the small holes in the plurality of belts 730. The casing is connected to a suction machine (not shown) to create a negative pressure inside the casing and generate a suction force on the surface of the belt 730 through which the electrode sheet 60 passes. In the suction mechanism, the mode of the suction mechanism is not limited to the above as long as the electrode sheet 60 can be adsorbed to the belt 730.

  In this way, by applying a suction force to the electrode sheet 60 being conveyed, the catalyst layer 20 is deformed, such as warping, as in the case where the electrode sheet 40 or the electrode sheet 60 is sandwiched in the first to sixth embodiments. Can be suppressed.

(Example)
Next, since it confirmed by experiment about suppression of deformation | transformation, such as curvature of a catalyst layer, it demonstrates below. In this example, the pore volume of the electrode catalyst is 2.16 cc / g: the peak value (maximum frequency) is obtained in the differential pore distribution curve obtained by the pore mode radius (nitrogen adsorption method (DH method)). A carbon support with a point void radius of 2.13 nm; and a BET specific surface area of 1596 m ² / g was used. The carrier is produced by the method described in JP-A-2009-35598.

  Further, using the above support, platinum (Pt) having an average particle radius of 1.15 nm as a catalyst metal was supported on the support so as to have a support rate of 50% by weight to obtain a catalyst powder. That is, 46 g of the carrier was immersed in 1000 g (platinum content: 46 g) of a dinitrodiammine platinum nitric acid solution having a platinum concentration of 4.6% by mass and stirred, and then 100 ml of 100% ethanol was added as a reducing agent. And it filtered and dried and obtained the catalyst powder whose loading rate is 50 weight%. Then, it hold | maintained at the temperature of 900 degreeC in hydrogen atmosphere for 1 hour, and obtained the catalyst powder.

  The catalyst powder prepared above mixed with ion-exchanged water and the ionomer dispersion (Nafion (registered trademark) D2020, EW1100 g / mol, manufactured by Dupont) as a polymer electrolyte were mixed with a weight ratio (I / C) was mixed to 1.3. Furthermore, the ratio of the weight ratio of the n-propyl alcohol solution as the solvent to the ion-exchanged water and the n-propyl alcohol solution was (the ion-exchanged water) / (the n-propyl alcohol solution) = 9/1, and the solid content ( A cathode catalyst ink was prepared by adding 11% by weight of Pt + carbon carrier + ionomer). Here, EW (Equivalent Weight) represents the equivalent weight of the exchange group having proton conductivity. The equivalent weight is the dry weight of ion exchange groups per equivalent of ion exchange groups, and is expressed in units of “g / eq”.

The catalyst ink prepared according to the above specifications was applied to a transfer sheet having a thickness of 100 μm containing PTFE using an applicator. The size of the catalyst layer is □ 50 mm × 50 mm. The target application weight is 0.35 mg-Pt / cm ² .

  A load was applied and restrained by sandwiching the catalyst ink and transfer sheet prepared above with a plate-like member made of SUS before heat treatment. Thereafter, heat treatment was performed in an oven at 180 ° C. for 30 minutes, and the above restraint was released at the timing when the temperature was cooled to room temperature.

  The catalyst layer was stored at room temperature in an air atmosphere, and the deflection of the catalyst layer was measured after a period of time (about one day) that seems to have reached an equilibrium state such as moisture absorption. The deflection was measured by placing the catalyst layer on a flat table and measuring the height from the installation surface of the transfer sheet with the catalyst layer on a scale.

  FIG. 12 is a table showing the shape, deformation, and the like after the catalyst layer is cooled by the method according to the example of the present invention or the comparative example. In this embodiment, two opposing sides of the rectangular catalyst layer are constrained as shown in FIG. 12 (2), or four sides of the rectangular catalyst layer are constrained as shown in FIG. 12 (3). . On the other hand, as shown in FIG. 12 (1), the comparative example was not restrained at all.

  In this experiment, heat treatment was performed at 180 ° C. for 30 minutes as described above, the amount of deflection of the catalyst layer after storage in the air atmosphere was measured, and the sides and corners of the rectangular catalyst layer before deformation were visually recognized. I confirmed that it was possible. Regarding the recognition of the side of the catalyst layer, the linearity of the original side before cooling can be maintained, and the corner of the catalyst layer is set to ○ when the location of the original corner can be estimated from two adjacent sides, In other cases, it was judged as x.

  As shown in FIG. 12, in the comparative example (1), it was confirmed that the shape in plan view was significantly deformed compared to (2) and (3). That is, in (1), it was confirmed that the catalyst layer was extremely deformed and it was difficult to recognize the original sides and corners of the catalyst layer.

  On the other hand, in the examples (2) and (3) corresponding to the examples, it can be confirmed that the shape of the catalyst layer in plan view is hardly deformed compared to (1), and the deflection amount is 20% compared to (1). It was confirmed that the original sides and corner positions could be recognized. Thus, it was confirmed that the deformation of the catalyst layer after cooling can be effectively suppressed by using the method according to the present embodiment.

In addition, this embodiment is not limited only to embodiment mentioned above, A various change is possible in a claim. In the above embodiment, the embodiment in which the catalyst ink is applied to a transfer sheet such as PTFE has been described. However, the present invention is not limited to this. In addition to the above, it may be applied directly to the electrolyte membrane, or may be applied to a gas diffusion layer (also referred to as GDL) constituting the MEA.
In the above description, the embodiment in which the outer portion of the electrode sheet than the catalyst layer is constrained during cooling has been described. However, it is not limited to this, You may make it restrain the electrode sheet 40 from the time of the heat processing which is a process before cooling to a cooling process. In the first embodiment, the embodiment in which the outer peripheries of two sides or four sides facing each other in the sheet-like electrode sheet 40 is constrained has been described. However, the present invention is not limited to this, and it may be configured to constrain the four corners of the electrode sheet 40 in addition to the above, as long as the outside of the catalyst layer is constrained.

10 Fuel cell,
11 MEA,
11a electrolyte membrane,
11b anode,
11c cathode,
110 application part,
120 heat treatment section,
130 restraint section,
131 tables,
132 mounting section,
133, 136 contact part,
134 movable parts,
135 support,
140 Laminating part,
20 catalyst ink (catalyst layer),
30, 50 sheet member,
40, 60 electrode sheet,
13, 14 Separator.

Claims (18)

A method for producing an electrode sheet, which is used in a membrane electrode assembly and has a catalyst layer containing an electrolyte formed on a sheet member,
Applying the catalyst layer to a sheet member to form the electrode sheet;
Heating the electrode sheet, then cooling in an air atmosphere,
The said electrode sheet is a manufacturing method of the electrode sheet cooled in the state which restrained the said sheet member at least in the case of the said cooling.   The said electrode sheet is a manufacturing method of the electrode sheet of Claim 1 restrained in the thickness direction of the said electrode sheet in the case of the said cooling.   The electrode sheet manufacturing method according to claim 1, wherein the restraint is performed by applying a load in a thickness direction of the electrode sheet.   The method for producing an electrode sheet according to any one of claims 1 to 3, wherein the electrode sheet is constrained at a position separated outward in the surface direction of the electrode sheet from the catalyst layer during the restraint. .   The said restraint is a manufacturing method of the electrode sheet of any one of Claims 1-4 performed by clamping the said electrode sheet. The electrode sheet has a polygonal shape with a plurality of sides,
The method of manufacturing an electrode sheet according to claim 6, wherein the restraint is performed by sandwiching two or more sides facing each other in the plurality of sides. The electrode sheet is formed in a sheet shape and has a polygonal shape with a plurality of sides,
The electrode sheet manufacturing method according to claim 5, wherein the restraint is performed by sandwiching a position separated in a surface direction of the electrode sheet by a plate-like member.   The electrode according to any one of claims 1 to 4, wherein the electrode sheet is formed and transported while being transported and restrained at both ends in a transverse direction intersecting the transport direction of the electrode sheet. Sheet manufacturing method.   The electrode sheet according to claim 8, wherein the electrode sheet is conveyed while being wound between the rail member and a rotatable roller, with the both ends of the electrode sheet wound around a rail member provided extending in the conveying direction. Manufacturing method.   The said electrode sheet is a manufacturing method of the electrode sheet of Claim 8 conveyed while being pinched | interposed by the roller and belt-shaped member which can rotate the said both ends in the said electrode sheet.   The method for producing an electrode sheet according to claim 8, wherein the electrode sheet is sandwiched and conveyed while being tensioned in the transverse direction.   The said restraint is a manufacturing method of the electrode sheet of Claim 5 performed by pinching the said electrode sheet using the frame member formed in frame shape. The electrode sheet is formed in a sheet shape and has a polygonal shape with a plurality of sides,
The electrode sheet manufacturing method according to claim 12, wherein the restraint is performed by sandwiching the plurality of sides of the electrode sheet using the frame member.   The electrode sheet manufacturing method according to claim 12, wherein the electrode sheet is formed in a long shape and conveyed, and conveyed while sandwiching an outer periphery of the electrode sheet using the frame member.   The said restraint is a manufacturing method of the electrode sheet of any one of Claims 1-4 performed by attracting | sucking the said electrode sheet.   The method for manufacturing an electrode sheet according to any one of claims 1 to 15, wherein the heating of the electrode sheet is performed at a temperature not lower than a glass transition temperature of the electrolyte and not higher than a decomposition temperature of the electrolyte. Release the restraint of the electrode sheet after the cooling,
The said cancellation | release is a manufacturing method of the electrode sheet of any one of Claims 1-16 performed below below the glass transition temperature of the electrolyte used for the said catalyst layer.   The sheet member is a transfer sheet used when transferring the electrolyte layer, a gas diffusion layer contained in the membrane electrode assembly and diffusing a fluid flowing in the catalyst layer, or the catalyst layer to the electrolyte membrane. Item 18. The method for producing an electrode sheet according to any one of Items 1 to 17.