JP2018190536A - Manufacturing method of polymer electrolyte with resin frame/electrode structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of polymer electrolyte with resin frame/electrode structure which allows for efficient manufacture of polymer electrolyte with resin frame/electrode structure.SOLUTION: A manufacturing method of polymer electrolyte with resin frame/electrode structure 10 includes a first bonding step, and a second bonding step. In the first bonding step, a first sheet-like member 56 and a resin frame member 24, provided with an adhesive layer 24c on one side, are thermo-compression bonded so that the outer peripheral part of the first sheet-like member 56 and the inner peripheral part 25 of the first face 24s1 of the resin frame member 24 are bonded. In the second bonding step, an anode electrode 20 and the resin frame member 24 are thermo-compression bonded so that the outer peripheral part of the anode electrode 20 and the inner peripheral part 25 in the second face 24s2 of the resin frame member 24 are bonded.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a method for producing an electrolyte membrane / electrode structure with a resin frame in which a resin frame member is provided on the outer periphery of the electrolyte membrane / electrode structure.

  In general, a polymer electrolyte fuel cell employs a polymer electrolyte membrane made of a polymer ion exchange membrane. The fuel cell includes an electrolyte membrane / electrode structure (MEA) in which an anode electrode is disposed on one surface of a solid polymer electrolyte membrane and a cathode electrode is disposed on the other surface of the solid polymer electrolyte membrane.

  The electrolyte membrane / electrode structure is sandwiched between separators (bipolar plates) to form a power generation cell (unit fuel cell). The power generation cells are used as, for example, an in-vehicle fuel cell stack by stacking a predetermined number of power generation cells.

  In recent years, in order to reduce the amount of relatively expensive solid polymer electrolyte membranes used and to protect thin polymer electrolyte membranes with low strength, MEA with a resin frame incorporating a resin frame member on the outer periphery has been adopted. (For example, refer to Patent Document 1).

JP 2008-71542 A

  By the way, in the manufacturing process of the MEA with a resin frame, the electrolyte membrane / electrode structure and the resin frame member are integrated by hot pressing.

  The present invention has been made in connection with the above-described prior art, and provides a method for producing an electrolyte membrane / electrode structure with a resin frame capable of efficiently producing an electrolyte membrane / electrode structure with a resin frame. For the purpose.

  In order to achieve the above object, a method for producing an electrolyte membrane / electrode structure with a resin frame according to the present invention includes a sheet-like member having a first electrode and an electrolyte membrane provided with the first electrode on one surface; Thermocompression-bonding a resin frame member provided with an opening and an adhesive layer on one side so as to join the outer peripheral part of the sheet-like member and the inner peripheral part on the one side of the resin frame member A first joining step, and a second joining in which the second electrode and the resin frame member are thermocompression-bonded so as to join the outer peripheral portion of the second electrode and the inner peripheral portion of the other surface of the resin frame member. And a process.

  The thermocompression bonding temperature in the second joining step is preferably higher than the thermocompression bonding temperature in the first joining step.

  In the second bonding step, it is preferable that the first electrode and the second electrode are thermocompression bonded through the electrolyte membrane in the opening.

  In the first bonding step, a frame-shaped mold that follows the shape of the outer peripheral portion of the first electrode is used, and the outer peripheral portion of the electrolyte membrane and the inner peripheral portion of the resin frame member overlap each other. It is preferable to perform thermocompression bonding by sandwiching from above and below.

  In the first joining step, it is preferable that the electrolyte membrane is thermocompression bonded to a plurality of frame member material sheets constituting the resin frame members.

  In the second joining step, it is preferable to perform thermocompression bonding in a state where the resin frame member joined to the sheet-like member is stacked on the second electrode.

  According to the method for manufacturing an electrolyte membrane / electrode structure with a resin frame of the present invention, the electrolyte membrane, the first electrode, the second electrode, and the resin frame member are not integrated by one thermocompression bonding, A first joining step for thermocompression bonding the sheet-like member having the first electrode and the resin frame member, and a second joining step for thermocompression bonding the resin frame member and the second electrode are performed. Therefore, a resin comprising an electrolyte membrane / electrode structure in which the first electrode and the second electrode are arranged on both sides of the electrolyte membrane, and a resin frame member joined to the outer periphery of the electrolyte membrane / electrode structure. The framed electrolyte membrane / electrode structure can be efficiently manufactured.

It is a disassembled perspective view of the electric power generation cell which comprises a fuel cell stack. It is the II-II sectional view taken on the line in FIG. FIG. 3A is a side view of the frame member material sheet unwound from the roll body. FIG. 3B is a plan view of the frame member material sheet unwound from the roll body. It is explanatory drawing of the 1st joining process of the manufacturing method of the electrolyte membrane-electrode structure with a resin frame which concerns on embodiment of this invention. It is explanatory drawing of the 2nd joining process of the manufacturing method of the electrolyte membrane and electrode structure with a resin frame which concerns on embodiment of this invention.

  Hereinafter, preferred embodiments of the method for producing an electrolyte membrane / electrode structure with a resin frame according to the present invention will be described with reference to the accompanying drawings.

  As shown in FIGS. 1 and 2, the power generation cell (fuel cell) 12 is disposed on both sides of an electrolyte membrane / electrode structure 10 with a resin frame (hereinafter referred to as “MEA 10 with a resin frame”) and an MEA 10 with a resin frame. The first separator 14 and the second separator 16 are provided. The power generation cell 12 is, for example, a horizontally long (or vertically long) rectangular polymer electrolyte fuel cell. The plurality of power generation cells 12 are stacked in, for example, an arrow A direction (horizontal direction) or an arrow C direction (gravity direction) to form the fuel cell stack 11. The fuel cell stack 11 is mounted on, for example, a fuel cell electric vehicle (not shown) as an in-vehicle fuel cell stack.

  In the power generation cell 12, the MEA 10 with a resin frame is sandwiched between the first separator 14 and the second separator 16. The first separator 14 and the second separator 16 have a horizontally long (or vertically long) rectangular shape. The first separator 14 and the second separator 16 are made of, for example, a steel plate, a stainless steel plate, an aluminum plate, a plating-treated steel plate, a metal plate whose surface is subjected to anticorrosion treatment, a carbon member, or the like.

  The MEA 10 with a resin frame includes an electrolyte membrane / electrode structure 10a (hereinafter referred to as “MEA 10a”) and a resin frame member 24 that is joined to the outer periphery of the MEA 10a and circulates around the outer periphery. The MEA 10 a includes an electrolyte membrane 18, an anode electrode 20 provided on one surface of the electrolyte membrane 18, and a cathode electrode 22 provided on the other surface of the electrolyte membrane 18. The anode electrode 20 constitutes one of the first electrode and the second electrode. The cathode electrode 22 constitutes the other of the first electrode and the second electrode.

  The electrolyte membrane 18 is, for example, a solid polymer electrolyte membrane (cation exchange membrane). The solid polymer electrolyte membrane is, for example, a thin film of perfluorosulfonic acid containing moisture. The electrolyte membrane 18 is sandwiched between the anode electrode 20 and the cathode electrode 22. The electrolyte membrane 18 can use an HC (hydrocarbon) based electrolyte in addition to a fluorine based electrolyte.

  The anode electrode 20 has a larger planar dimension (outer dimension) than the electrolyte membrane 18 and the cathode electrode 22. Instead of the above configuration, the anode electrode 20 may be configured to have a smaller planar dimension than the electrolyte membrane 18 and the cathode electrode 22.

  The anode electrode 20 includes a first electrode catalyst layer 20a joined to one surface 18a of the electrolyte membrane 18, and a first gas diffusion layer 20b laminated on the first electrode catalyst layer 20a. The first electrode catalyst layer 20 a and the first gas diffusion layer 20 b have the same planar dimensions as each other, and are set to have a larger planar dimension than the electrolyte membrane 18 and the cathode electrode 22.

  The cathode electrode 22 has a second electrode catalyst layer 22a joined to the surface 18b of the electrolyte membrane 18, and a second gas diffusion layer 22b laminated on the second electrode catalyst layer 22a. The second electrode catalyst layer 22 a and the second gas diffusion layer 22 b have the same planar dimensions as each other and are set to the same planar dimensions as the electrolyte membrane 18. Therefore, the outer peripheral end 22e of the cathode electrode 22 is in the same position as the outer peripheral end 18e of the electrolyte membrane 18 in the surface direction of the electrolyte membrane 18 (the direction of arrow C in FIG. 2).

  The cathode electrode 22 is set to have a smaller planar dimension than the anode electrode 20. The outer peripheral end 22 e of the cathode electrode 22 and the outer peripheral end 18 e of the electrolyte membrane 18 are located inward of the outer peripheral end 20 e of the anode electrode 20.

  The cathode electrode 22 may be set to have a larger planar dimension than the anode electrode 20, and the outer peripheral end 22 e of the cathode electrode 22 may be located outward from the outer peripheral end 20 e of the anode electrode 20. Alternatively, the anode electrode 20 and the cathode electrode 22 are set to have the same planar dimension, and the outer peripheral end 20e of the anode electrode 20 and the outer peripheral end 22e of the cathode electrode 22 are in the plane direction of the electrolyte membrane 18 (the direction of arrow C in FIG. 2). ) In the same position.

  The first electrode catalyst layer 20a is formed, for example, by uniformly applying porous carbon particles having a platinum alloy supported on the surface thereof to the surface of the first gas diffusion layer 20b together with an ion conductive polymer binder. The second electrode catalyst layer 22a is formed, for example, by applying porous carbon particles having a platinum alloy supported on the surface thereof to the surface of the second gas diffusion layer 22b together with an ion conductive polymer binder.

  The first gas diffusion layer 20b and the second gas diffusion layer 22b are formed of carbon paper, carbon cloth, or the like. The planar dimension of the second gas diffusion layer 22b is set smaller than the planar dimension of the first gas diffusion layer 20b. The first electrode catalyst layer 20 a and the second electrode catalyst layer 22 a are formed on both surfaces of the electrolyte membrane 18.

  The resin frame member 24 has two frame-like sheets having different thicknesses. Specifically, the resin frame member 24 includes a first frame-shaped sheet 24a in which an inner peripheral portion 24an is bonded to the outer peripheral portion of the MEA 10a, and a second frame-shaped sheet 24b bonded to the first frame-shaped sheet 24a. Have. The first frame sheet 24a and the second frame sheet 24b are joined to each other in the thickness direction by an adhesive layer 24c made of an adhesive 24d. The second frame-like sheet 24b is joined to the outer periphery of the first frame-like sheet 24a. Accordingly, the outer peripheral portion of the resin frame member 24 is configured to be thicker than the inner peripheral portion 25 of the resin frame member 24. The first frame-like sheet 24a and the second frame-like sheet 24b may have the same thickness.

  The first frame-like sheet 24a and the second frame-like sheet 24b are made of a resin material. As a constituent material of the first frame-like sheet 24a and the second frame-like sheet 24b, for example, PPS (polyphenylene sulfide), PPA (polyphthalamide), PEN (polyethylene naphthalate), PES (polyethersulfone), LCP (Liquid crystal polymer), PVDF (polyvinylidene fluoride), silicone resin, fluororesin, m-PPE (modified polyphenylene ether resin), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), modified polyolefin, and the like.

  The inner peripheral portion 25 of the resin frame member 24 (the inner peripheral portion 24an of the first frame-like sheet 24a) is disposed between the outer peripheral portion 20c of the anode electrode 20 and the outer peripheral portion 22c of the cathode electrode 22. Specifically, the inner peripheral portion 25 of the resin frame member 24 is sandwiched between the outer peripheral portion 18 c of the electrolyte membrane 18 and the outer peripheral portion 20 c of the anode electrode 20. The inner peripheral portion 25 of the resin frame member 24 and the outer peripheral portion 18c of the electrolyte membrane 18 are joined via an adhesive layer 24c. The inner peripheral portion 25 of the resin frame member 24 may be sandwiched between the electrolyte membrane 18 and the cathode electrode 22.

  The anode electrode 20 described above is provided with a step at a position corresponding to the inner peripheral edge 24ae of the first frame-like sheet 24a. Specifically, the anode electrode 20 has an inclined region 21 c that is inclined with respect to the electrolyte membrane 18 between a region 21 a that overlaps the inner peripheral portion 24 an of the first frame-shaped sheet 24 a and a region 21 b that overlaps the electrolyte membrane 18. . Therefore, the first electrode catalyst layer 20 a and the first gas diffusion layer 20 b are inclined with respect to the electrolyte membrane 18 in the inclined region 21 c.

  In the anode electrode 20, the surface on the first separator 14 side of the region 21 a that overlaps the inner peripheral portion 24 an of the first frame-like sheet 24 a is more than the surface on the first separator 14 side of the region 21 b that overlaps the electrolyte membrane 18. It is in a position away from 18.

  On the other hand, the cathode electrode 22 is formed in a flat shape from the region 23b overlapping the electrolyte membrane 18 to the region 23a overlapping the inner peripheral portion 24an of the first frame-like sheet 24a. Therefore, the second electrode catalyst layer 22a and the second gas diffusion layer 22b are parallel to the electrolyte membrane 18 from the region 23b overlapping the electrolyte membrane 18 to the region 23a overlapping the inner peripheral portion 24an of the first frame-like sheet 24a. is there.

  Unlike the above configuration, the anode electrode 20 is formed in a flat shape from the region 21b that overlaps the electrolyte membrane 18 to the region 21a that overlaps the inner peripheral portion 24an of the first frame-like sheet 24a, and the cathode electrode 22 is the electrolyte. An inclined region inclined with respect to the electrolyte membrane 18 may be provided between the region 23b overlapping the membrane 18 and the region 23a overlapping the inner peripheral portion 24an of the first frame-like sheet 24a.

  The second frame-like sheet 24b is joined to the outer periphery of the first frame-like sheet 24a by an adhesive 24d. The inner peripheral edge 24be of the second frame-shaped sheet 24b is located outward (in the direction away from the MEA 10a) from the inner peripheral edge 24ae of the first frame-shaped sheet 24a, and the outer peripheral edge 20e of the anode electrode 20 and the cathode electrode 22 are located. It is located outward from the outer peripheral end 22e.

  The adhesive layer 24c is provided over the entire surface 24as of the first frame-like sheet 24a on the second frame-like sheet 24b side (cathode side). Therefore, the adhesive layer 24 c is also provided on the inner peripheral portion 25. As the adhesive 24d constituting the adhesive layer 24c, for example, a liquid seal or a hot melt agent is provided. Note that the adhesive 24d is not limited to liquid, solid, thermoplasticity, thermosetting, or the like.

  The resin frame member 24 is not limited to a configuration in which the first frame-shaped sheet 24a and the second frame-shaped sheet 24b are bonded via the adhesive layer 24c, and may be a member integrally formed as a whole. Further, the resin frame member 24 is not limited to a stepped shape having a relatively thin inner peripheral portion and a relatively thick outer peripheral portion, and has no step from the inner peripheral portion to the outer peripheral portion (substantially flat). Shape).

  As shown in FIG. 1, one end edge of the power generation cell 12 in the direction of arrow B (horizontal direction) communicates with each other in the direction of arrow A, which is the stacking direction. A hole 32a and a fuel gas outlet communication hole 34b are provided. The oxidant gas inlet communication hole 30a supplies an oxidant gas, for example, an oxygen-containing gas, while the cooling medium inlet communication hole 32a supplies a cooling medium. The fuel gas outlet communication hole 34b discharges fuel gas, for example, hydrogen-containing gas. The oxidant gas inlet communication hole 30a, the cooling medium inlet communication hole 32a, and the fuel gas outlet communication hole 34b are arranged in the direction of arrow C (vertical direction).

  The other end edge of the power generation cell 12 in the direction of arrow B communicates with each other in the direction of arrow A, the fuel gas inlet communication hole 34a for supplying fuel gas, the cooling medium outlet communication hole 32b for discharging the cooling medium, and the oxidation An oxidant gas outlet communication hole 30b for discharging the oxidant gas is provided. The fuel gas inlet communication hole 34a, the cooling medium outlet communication hole 32b, and the oxidant gas outlet communication hole 30b are arranged in the direction of arrow C.

  An oxidant gas flow path 36 communicating with the oxidant gas inlet communication hole 30a and the oxidant gas outlet communication hole 30b is provided on the surface 16a of the second separator 16 facing the MEA 10 with a resin frame. Specifically, the oxidant gas flow path 36 is formed between the second separator 16 and the MEA 10 with a resin frame. The oxidant gas flow channel 36 has a plurality of linear flow channel grooves (or wavy flow channel grooves) extending in the arrow B direction.

  A fuel gas passage 38 communicating with the fuel gas inlet communication hole 34a and the fuel gas outlet communication hole 34b is provided on the surface 14a of the first separator 14 facing the MEA 10 with the resin frame. Specifically, the fuel gas passage 38 is formed between the first separator 14 and the MEA 10 with a resin frame. The fuel gas flow path 38 has a plurality of straight flow path grooves (or wavy flow path grooves) extending in the direction of arrow B.

  Between the surface 14b of the first separator 14 and the surface 16b of the second separator 16 adjacent to each other, a cooling medium flow path 40 communicating with the cooling medium inlet communication hole 32a and the cooling medium outlet communication hole 32b is indicated by an arrow B. It is formed extending in the direction.

  As shown in FIG. 2, the surface 14 a of the first separator 14 (surface facing the MEA 10 with a resin frame) is provided with a plurality of convex portions 39 that form the fuel gas flow path 38. The convex portion 39 bulges toward the anode electrode 20 and contacts the anode electrode 20. A plurality of convex portions 37 forming the oxidant gas flow path 36 are provided on the surface 16a of the second separator 16 (the surface facing the MEA 10 with a resin frame). The convex portion 37 bulges toward the cathode electrode 22 side and contacts the cathode electrode 22. The MEA 10 a is sandwiched between the convex portions 37 and 39.

  The surface 14a of the first separator 14 is provided with a first seal line 42 (metal bead seal) that goes around the outer periphery of the first separator 14. The first seal line 42 bulges toward the resin frame member 24 and abuts on the first frame sheet 24a (a region overlapping with the second frame sheet 24b) in an airtight and liquid tight manner. The first seal line 42 has an outer bead portion 42a and an inner bead portion 42b provided inside the outer bead portion 42a.

  The inner bead portion 42b goes around the fuel gas flow path 38, the fuel gas inlet communication hole 34a, and the fuel gas outlet communication hole 34b and makes them communicate with each other. The cross-sectional shape of each bead part 42a, 42b is a taper shape toward the front end side (resin frame member 24 side). The tip of each bead part 42a, 42b has a flat shape (may be a curved shape).

  A flow path 38 a formed between the first separator 14 and the resin frame member 24 on the inner side (MEA 10 a side) than the first seal line 42 communicates with the fuel gas flow path 38. Accordingly, the fuel gas is supplied to the flow path 38a.

  The surface 16a of the second separator 16 is provided with a second seal line 44 (metal bead seal) that goes around the outer periphery of the second separator 16. The second seal line 44 bulges toward the resin frame member 24 and abuts against the second frame sheet 24b in an airtight and liquid tight manner. The first seal line 42 and the second seal line 44 oppose each other via the resin frame member 24. The resin frame member 24 is sandwiched between the first seal line 42 and the second seal line 44. The second seal line 44 includes an outer bead portion 44a and an inner bead portion 44b provided inside the outer bead portion 44a.

  The inner bead portion 44b circulates the oxidant gas flow path 36, the oxidant gas inlet communication hole 30a, and the oxidant gas outlet communication hole 30b and communicates them. The cross-sectional shape of each bead part 44a and 44b is a taper shape toward the front end side (resin frame member 24 side). The tip of each bead part 44a, 44b has a flat shape (may be a curved shape).

  A flow path 36 a formed between the second separator 16 and the resin frame member 24 on the inner side (MEA 10 a side) than the second seal line 44 communicates with the oxidant gas flow path 36. Therefore, the oxidizing gas is supplied to the flow path 36a.

  The operation of the fuel cell stack 11 including the power generation cell 12 configured as described above will be described below.

  As shown in FIG. 1, an oxidant gas such as an oxygen-containing gas is supplied to the oxidant gas inlet communication hole 30a, and a fuel gas such as a hydrogen-containing gas is supplied to the fuel gas inlet communication hole 34a. The Further, a cooling medium such as pure water, ethylene glycol, or oil is supplied to the cooling medium inlet communication hole 32a.

  Therefore, the oxidant gas is introduced from the oxidant gas inlet communication hole 30a into the oxidant gas flow path 36 of the second separator 16, moves in the direction of arrow B, and is supplied to the cathode electrode 22 of the MEA 10a. On the other hand, the fuel gas is introduced into the fuel gas flow path 38 of the first separator 14 from the fuel gas inlet communication hole 34a. The fuel gas moves in the direction of arrow B along the fuel gas flow path 38 and is supplied to the anode electrode 20 of the MEA 10a.

  Therefore, in the MEA 10a, the oxidant gas supplied to the cathode electrode 22 and the fuel gas supplied to the anode electrode 20 are consumed by an electrochemical reaction in the second electrode catalyst layer 22a and the first electrode catalyst layer 20a. Power generation.

  Next, in FIG. 1, the oxidant gas consumed by being supplied to the cathode electrode 22 is discharged in the direction of arrow A along the oxidant gas outlet communication hole 30b. Similarly, the fuel gas consumed by being supplied to the anode electrode 20 is discharged in the direction of arrow A along the fuel gas outlet communication hole 34b.

  The cooling medium supplied to the cooling medium inlet communication hole 32a is introduced into the cooling medium flow path 40 between the first separator 14 and the second separator 16, and then flows in the direction of arrow B. The cooling medium is discharged from the cooling medium outlet communication hole 32b after cooling the MEA 10a.

  Subsequently, the manufacturing method of MEA 10 with a resin frame which concerns on this embodiment is demonstrated below.

  The manufacturing method of the MEA 10 with a resin frame includes the first sheet-like member 56 having the first electrode (the cathode electrode 22 in the present embodiment) and the electrolyte membrane 18 as one electrode of the MEA 10 with a resin frame, the resin frame member 24, A first joining step in which the second electrode (in this embodiment, the anode electrode 20), which is the other electrode of the resin frame-attached MEA 10, and the resin frame member 24 are joined by thermocompression bonding. Process.

  In the first joining step, for example, as shown in FIGS. 3A and 3B, a frame member material sheet 50 constituting a plurality of resin frame members 24 is used. Specifically, the frame member material sheet 50 is a band-shaped member having a configuration in which a plurality of resin frame members 24 are arranged in series, as shown in FIG. 3B. A plurality of openings 24 e forming the inner peripheral edge 24 ae of the resin frame member 24 are provided at intervals in the length direction of the frame member material sheet 50.

  The frame member material sheet 50 is unwound from the roll body 52 (first roll body) and supplied to equipment for performing the first joining step (first joining device 54 shown in FIG. 4). In the roll body 52, the frame member material sheet 50 and an unillustrated interlayer film (protective film) are wound in a roll shape in a state of being overlapped. As the frame member material sheet 50 is unwound from the roll body 52, the interlayer film is also unwound. The unrolled interlayer film is wound up by a winding roll (not shown). The frame member material sheet 50 is supplied to the first joining device 54 of FIG. 4 with the surface on which the adhesive layer 24c (FIG. 2) is provided facing upward.

  As shown in FIG. 4, the first joining device 54 is supplied with a rectangular first sheet-like member 56 having the cathode electrode 22 and the electrolyte membrane 18. The first sheet-like member 56 includes a first support sheet 58, a cathode electrode 22 supported by the first support sheet 58, and an electrolyte membrane 18 provided with the cathode electrode 22 on one surface. The first support sheet 58 is made of, for example, carbon paper.

  For example, a roll body (hereinafter referred to as “second roll body”) in which a strip-shaped multilayer sheet composed of the first support sheet 58, the cathode electrode 22, and the electrolyte membrane 18 is wound in a roll shape is used. The multilayer sheet is unwound from the second roll body. Then, the unrolled multilayer sheet is cut at a predetermined interval by a cutter (for example, a roller cutter), whereby a rectangular first sheet-like member 56 cut out to a predetermined dimension is obtained.

  The first sheet-like member 56 is supplied to the first joining device 54 with the electrolyte membrane 18 facing downward, and is placed on the resin frame member 24 (frame member material sheet 50) (first sheet-like member). Placement process). In this case, in the first sheet-like member 56, the electrolyte membrane 18 faces the opening 24 e of the resin frame member 24, and the outer peripheral portion of the electrolyte membrane 18 extends over the entire inner periphery 25 of the resin frame member 24. It arrange | positions on the resin frame member 24 so that it may overlap.

  In the first joining step, the first sheet-like member 56 and the resin frame member 24 are connected to the outer periphery of the electrolyte membrane 18 and the inner periphery of the first surface 24s1 (surface on which the adhesive layer 24c is provided) of the resin frame member 24. Thermocompression bonding is performed so that the portion 25 is joined to the entire circumference. Specifically, in the first bonding step, an electrolyte membrane is used by using a first bonding device 54 including a frame-shaped mold (upper mold 54a and lower mold 54b) along the shape of the outer peripheral portion of the cathode electrode 22. A portion where the outer peripheral portion 18 and the inner peripheral portion 25 of the resin frame member 24 overlap is sandwiched from above and below, and thermocompression bonding (heating and pressing) is performed.

  In the thermocompression bonding of the first sheet-like member 56 and the resin frame member 24 in the first joining step, the first sheet-like member 56 is resin frame before the second joining step is started after the first joining step. It is only necessary to obtain a bonding force that does not move with respect to the member 24. That is, the thermocompression bonding in the first bonding step is temporary pressure bonding (temporary fixing) in which the first sheet-like member 56 and the resin frame member 24 are bonded relatively weakly. The thermocompression bonding temperature in the first joining step is, for example, 90 to 110 ° C., and the pressing time is about several seconds.

  As shown in FIG. 5, the first sheet-like member 56 and the resin frame member 24 (hereinafter referred to as “intermediate joined body 59”) joined to each other in the first joining step are installed in the second joining step (second To the joining device 60). The second bonding apparatus 60 includes a table 62 that is a workpiece holding jig, and an upper mold 64a and a lower mold 64b that heat and press the intermediate bonded body 59 and the anode electrode 20 from above and below.

  The table 62 is formed with a rectangular work holding groove 63 having a support surface 63 a (step part) and a rectangular hole 66 communicating with the work holding groove 63. A rectangular cushion pad 68 (support member) having an outer dimension larger than that of the hole 66 is placed on the support surface 63 a so as to cover the hole 66. The hole 66 is opened at the lower surface 62b of the table 62, and the lower mold 64b is inserted therein.

  The upper mold 64a and the lower mold 64b are spaced apart from each other in the vertical direction, are disposed to face each other via the work holding groove 63, and are configured to be movable in the vertical direction. The opening dimension of the hole 66 and the outer diameter dimension of the pressing surface 65b of the lower mold 64b are the outer dimension of the first sheet-like member 56 (the cathode electrode 22 and the electrolyte membrane 18) and the outer dimension of the second sheet-like member 72 described later. Greater than dimensions. The outer dimension of the pressing surface 65 a of the upper mold 64 a is larger than the opening 24 e of the resin frame member 24 and slightly smaller than the outer dimension of the first sheet-like member 56.

  For example, a roll body (hereinafter referred to as “third roll body”) in which a strip-shaped multilayer sheet composed of the second support sheet 70 and the anode electrode 20 is wound in a roll shape is used. A multilayer sheet is unwound from the third roll body. Then, the unrolled multilayer sheet is cut at a predetermined interval by a cutter (for example, a roller cutter), whereby a rectangular second sheet-like member 72 cut out to a predetermined dimension is obtained. In the second sheet-like member 72, the anode electrode 20 is superimposed on the second support sheet 70. The second support sheet 70 is made of, for example, carbon paper.

  The second sheet-like member 72 is supplied to the second bonding apparatus 60 with the anode electrode 20 facing upward, and is placed on the cushion pad 68 (second sheet-like member arranging step). In this case, the 2nd sheet-like member 72 is arrange | positioned in the range of the hole part 66 by planar view. A groove for positioning the second sheet-like member 72 is preferably provided on the upper surface of the cushion pad 68. Since the second sheet-like member 72 is supported by the cushion pad 68, it does not fall into the hole 66.

  Next, the intermediate joined body 59 (the first sheet-like member 56 and the resin frame member 24) obtained by the first joining step is placed on the second sheet-like member 72. In this case, in the intermediate joined body 59, the anode electrode 20 faces the opening 24 e of the resin frame member 24, and the outer peripheral portion of the anode electrode 20 is entirely surrounded by the inner peripheral portion 25 on the second surface 24 s 2 of the resin frame member 24. It arrange | positions on the 2nd sheet-like member 72 so that it may overlap. Thereby, the outer periphery of the first sheet-like member 56 (the outer periphery of the electrolyte membrane 18) and the outer periphery of the second sheet-like member 72 (the outer periphery of the anode electrode 20) are the inner periphery of the resin frame member 24. 25 to overlap each other.

  In the second bonding step, the anode electrode 20 and the resin frame member 24 are bonded to the outer peripheral portion of the anode electrode 20 and the inner peripheral portion 25 of the second surface 24s2 of the resin frame member 24 over the entire periphery. Thermocompression bonded to. Specifically, in the second bonding step, the outer peripheral portion of the electrolyte membrane 18, the inner peripheral portion 25 of the resin frame member 24, and the anode electrode 20 are formed by the upper mold 64 a and the lower mold 64 b of the second bonding apparatus 60. A portion where the outer peripheral portion overlaps is sandwiched from above and below and thermocompression-bonded (heating and pressing). In this case, in the second bonding step, the cathode electrode 22 and the anode electrode 20 are thermocompression bonded through the opening 24e of the resin frame member 24.

  The MEA 10a (FIG. 2) in which the cathode electrode 22 and the anode electrode 20 are disposed on both sides of the electrolyte membrane 18 is obtained by the second bonding step, and the resin frame member 24 (frame member material sheet 50 is formed on the outer periphery of the MEA 10a. ) Are integrated by joining.

  The thermocompression bonding in the second bonding step is a main pressure bonding in which the intermediate bonded body 59 and the second sheet-like member 72 are firmly bonded to obtain a state in which the resin frame member 24 is integrated with the outer peripheral portion of the MEA 10a. . Therefore, the bonding strength by thermocompression bonding in the second bonding step is higher than the bonding strength by thermocompression bonding in the first bonding step. The thermocompression bonding temperature in the second joining step is, for example, 160 to 180 ° C. The pressing time in the second bonding step is preferably longer than the pressing time in the first bonding step.

  After the second joining step, the frame member material sheet 50 integrated with the MEA 10a is cut into a rectangular shape having a predetermined size, whereby the MEA 10 with a resin frame shown in FIG. 1 is obtained.

  In this case, the manufacturing method of MEA 10 with a resin frame according to the present embodiment has the following effects.

  In the manufacturing method of the MEA 10 with a resin frame, the first sheet-like member 56 having the cathode electrode 22 and the electrolyte membrane 18 and the resin frame member 24 in which the adhesive layer 24c is provided on the first surface 24s1 are formed into the first sheet-like shape. A first joining step (FIG. 4) in which the outer peripheral portion of the member 56 and the inner peripheral portion 25 on the first surface 24 s 1 of the resin frame member 24 are joined, and the anode electrode 20 and the resin frame member 24. And a second joining step (FIG. 5) in which the outer peripheral portion of the anode electrode 20 and the inner peripheral portion 25 on the second surface 24s2 of the resin frame member 24 are joined by thermocompression bonding.

  Therefore, according to the manufacturing method of the MEA 10 with a resin frame, the electrolyte membrane 18, the cathode electrode 22, the anode electrode 20, and the resin frame member 24 are not integrated by one thermocompression bonding, but the electrolyte membrane 18 and the cathode electrode 22 are integrated. The 1st joining process which thermocompression-bonds the 1st sheet-like member 56 which has these, and the resin frame member 24, and the 2nd joining process of thermocompression-bonding the resin frame member 24 and the anode electrode 20 are performed. For this reason, the MEA 10 with a resin frame including the MEA 10a in which the cathode electrode 22 and the anode electrode 20 are disposed on both sides of the electrolyte membrane 18 and the resin frame member 24 joined to the outer peripheral portion of the MEA 10a is efficiently manufactured. It becomes possible to do.

  The thermocompression bonding temperature in the second joining process is higher than the thermocompression bonding temperature in the first joining process. As a result, since the first bonding process requires simple thermocompression bonding, the time required for the first bonding process can be shortened, and sufficient bonding strength can be obtained in the second bonding process.

  In the first joining step, the electrolyte membrane 18 (first sheet-like member) in which the cathode electrode 22 is provided on one side of the frame member material sheet 50 (FIGS. 3A and 3B) constituting the resin frame members 24 for a plurality of pieces. 56) is thermocompression bonded. Thereby, since the 1st sheet-like member 56 can be continuously conveyed to a 2nd joining process (2nd joining apparatus 60), it becomes possible to manufacture MEA10 with a resin frame still more efficiently.

  In the second bonding step, the resin frame member 24 (intermediate bonded body 59) bonded to the first sheet-like member 56 is superposed on the anode electrode 20 from above and below. As a result, the anode electrode 20 is placed on the table 62, and the resin frame member 24 joined to the first sheet-like member 56 is placed thereon, so that the positions of the resin frame member 24 and the anode electrode 20 can be accurately and easily set. Thermocompression bonding can be performed in a state matched to the above.

  The first sheet-like member 56 may be provided with the anode electrode 20 instead of the cathode electrode 22, and the second sheet-like member 72 may be provided with the cathode electrode 22 instead of the anode electrode 20. In this case, in the first bonding step, the outer peripheral portion of the electrolyte membrane 18 provided with the anode electrode 20 on one surface is bonded to the inner peripheral portion 25 of the first surface 24s1 of the resin frame member 24 by thermocompression bonding. In the second bonding step, the outer peripheral portion of the cathode electrode 22 is bonded to the inner peripheral portion 25 of the second surface 24s2 of the resin frame member 24 by thermocompression bonding.

  In this embodiment, each cell cooling structure is used in which cells that sandwich one MEA with two separators are stacked and a cooling medium is circulated between the cells. A so-called thinning cooling structure in which a cooling medium is circulated for each of a plurality of cells may be employed. At that time, the cell includes three or more separators and two or more MEAs.

  The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

DESCRIPTION OF SYMBOLS 10 ... Electrolyte membrane / electrode structure with resin frame 10a ... Electrolyte membrane / electrode structure 12 ... Power generation cell 20 ... Anode electrode 22 ... Cathode electrode 24 ... Resin frame member 24c ... Adhesive layer

Claims (6)

A sheet-like member having a first electrode and an electrolyte membrane having the first electrode provided on one surface, and a resin frame member having an opening and an adhesive layer provided on one surface, the sheet-like member. A first bonding step of thermocompression bonding so as to bond the outer peripheral portion of the resin frame member and the inner peripheral portion of the one surface of the resin frame member;
A second joining step of thermocompression bonding the second electrode and the resin frame member so as to join the outer peripheral portion of the second electrode and the inner peripheral portion of the other surface of the resin frame member;
A method for producing an electrolyte membrane / electrode structure with a resin frame, wherein: In the manufacturing method of the electrolyte membrane and electrode structure with a resin frame of Claim 1,
The thermocompression bonding temperature in the second joining step is higher than the thermocompression bonding temperature in the first joining step.
A method for producing an electrolyte membrane / electrode structure with a resin frame, wherein: In the method for producing an electrolyte membrane / electrode structure with a resin frame according to claim 1 or 2,
In the second bonding step, the first electrode and the second electrode are thermocompression bonded through the electrolyte membrane in the opening.
A method for producing an electrolyte membrane / electrode structure with a resin frame, wherein: In the manufacturing method of the electrolyte membrane and electrode structure with a resin frame of any one of Claims 1-3,
In the first bonding step, a frame-shaped mold that follows the shape of the outer peripheral portion of the first electrode is used, and the outer peripheral portion of the electrolyte membrane and the inner peripheral portion of the resin frame member overlap each other. Sandwiched from above and below and thermocompression bonded,
A method for producing an electrolyte membrane / electrode structure with a resin frame, wherein: In the manufacturing method of the electrolyte membrane and electrode structure with a resin frame of any one of Claims 1-4,
In the first joining step, the electrolyte membrane is thermocompression-bonded to a frame member material sheet constituting the resin frame member for a plurality of times.
A method for producing an electrolyte membrane / electrode structure with a resin frame, wherein: In the manufacturing method of the electrolyte membrane and electrode structure with a resin frame of any one of Claims 1-5,
In the second joining step, the resin frame member joined to the sheet-like member is thermocompression bonded on the second electrode.
A method for producing an electrolyte membrane / electrode structure with a resin frame, wherein:

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