JP2017130331A - Manufacturing method for mea with resin frame - Google Patents

Abstract

PROBLEM TO BE SOLVED: To firmly and surely bond a step MEA and a resin frame member by a simple step.SOLUTION: A step MEA10a is manufactured by setting a cathode electrode 22 and an anode electrode 20 while sandwiching a solid polymer electrolyte membrane 18. An outer peripheral surface 22ae of a second electrode catalyst layer 22a is exposed from an outer peripheral end part of a second gas diffusion layer 22b. An outer peripheral surface 18be of the solid polymer electrolyte membrane 18 is exposed from the outer peripheral end part of the second electrode catalyst layer 22a. Adhesive agent 26aa and 26ab are coated to the outer peripheral surface 22ae of the second electrode catalyst layer 22a, and thereafter, the step MEA10a and a resin frame member 24 are bonded by compression and a heating treatment.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a method for producing an MEA with a resin frame for a fuel cell, comprising: a step MEA having a solid polymer electrolyte membrane sandwiched between a first electrode and a second electrode; and a resin frame member joined to the outer periphery of the step MEA. About.

  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. Yes. The anode electrode and the cathode electrode each have a catalyst layer (electrode catalyst layer) and a gas diffusion layer (porous carbon).

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

  In the electrolyte membrane / electrode structure, one gas diffusion layer is set to a plane size smaller than that of the solid polymer electrolyte membrane, and the other gas diffusion layer is set to substantially the same plane size as the solid polymer electrolyte membrane. The so-called step MEA may be configured. At that time, in order to reduce the amount of the relatively expensive solid polymer electrolyte membrane used and to protect the solid polymer electrolyte membrane having a thin film shape and low strength, an MEA with a resin frame incorporating a resin frame member is adopted. Has been.

  For example, an electrolyte membrane / electrode structure with a resin frame disclosed in Patent Document 1 is known. In this electrolyte membrane / electrode structure with a resin frame, the outer peripheral edge of the solid polymer electrolyte membrane on the stepped portion side of the step MEA and the inner peripheral protrusion on the stepped side of the resin frame member are mutually bonded by an adhesive. It is fixed.

Japanese Patent Application Laid-Open No. 2014-017150

  By the way, when an adhesive is applied to the outer peripheral edge of the solid polymer electrolyte membrane, an adhesive reaction between the adhesive and the solid polymer electrolyte membrane proceeds with the passage of time. For this reason, when the solid polymer electrolyte membrane and the resin frame member are pressure-bonded to spread the adhesive, a clear interface may occur between the part where the adhesion reaction has progressed and the unreacted part. Therefore, when the adhesive is pressurized and heated to be cured and an adhesive layer is formed, the adhesive layer is easily peeled off at the interface, and there is a problem that the adhesive strength is reduced.

  This invention solves this kind of subject, and provides the manufacturing method of MEA with a resin frame which can adhere | attach a level | step difference MEA and a resin frame member firmly and reliably by a simple process. Objective.

  The present invention relates to a method for manufacturing an MEA with a resin frame for a fuel cell having a step MEA and a resin frame member. In the step MEA, a first electrode is provided on one surface of the solid polymer electrolyte membrane, a second electrode is provided on the other surface of the solid polymer electrolyte membrane, and a plane of the first electrode is provided. The dimension is set to be larger than the planar dimension of the second electrode.

  The second electrode includes a catalyst layer provided on the other surface with the outer peripheral surface of the solid polymer electrolyte membrane exposed, and a gas provided on the catalyst layer with the outer peripheral surface of the catalyst layer exposed. A diffusion layer is provided. The resin frame member is joined to the outer peripheral surface of the solid polymer electrolyte membrane exposed to the outside of the second electrode.

  In this manufacturing method, the first electrode is provided on one surface of the solid polymer electrolyte membrane, and the outer peripheral surface of the catalyst layer is protruded from the outer peripheral end of the gas diffusion layer on the other surface of the solid polymer electrolyte membrane. Thus, the step MEA is manufactured by providing the second electrode. And while shape | molding a resin frame member and apply | coating an adhesive agent to the outer peripheral surface of a catalyst layer, the level | step difference MEA and the said resin frame are overlapped with the level | step difference MEA and the said resin frame member, and are pressurized and heated. The member is joined.

  Further, in this manufacturing method, the adhesive is disposed on the catalyst layer in contact with the outer peripheral end surface of the gas diffusion layer, and on the catalyst layer, the adhesive is disposed on the outer peripheral end portion of the catalyst layer. It is preferably applied to two bonding lines.

  Furthermore, in this production method, the adhesive is preferably applied from the outer peripheral surface of the catalyst layer to the exposed portion of the solid polymer electrolyte membrane. At that time, the area of the adhesive applied to the exposed portion of the solid polymer electrolyte membrane is preferably set to 60% or less of the bonded area at the exposed portion.

  According to the present invention, when the step MEA and the resin frame member are bonded with an adhesive, the adhesive is applied to the outer peripheral surface of the catalyst layer protruding outward from the outer peripheral surface of the gas diffusion layer constituting the second electrode. It has been applied. For this reason, it is possible to shorten the time during which the adhesive and the solid polymer electrolyte membrane are in contact with each other as much as possible, and it is possible to reduce the variation in adhesion quality. Therefore, the step MEA and the resin frame member can be firmly and reliably bonded by a simple process.

It is principal part disassembled perspective explanatory drawing of the polymer electrolyte power generation cell in which MEA with a resin frame to which the manufacturing method of the present invention is applied is incorporated. It is II-II sectional view explanatory drawing in FIG. 1 of the said electric power generation cell. It is explanatory drawing at the time of forming CCM which comprises the said MEA with a resin frame in the said manufacturing method. In 1st manufacturing method, it is explanatory drawing at the time of applying an adhesive agent to level | step difference MEA. It is explanatory drawing at the time of joining a resin frame member to the said level | step difference MEA in the said 1st manufacturing method. In the manufacturing method of a comparative example, it is explanatory drawing at the time of applying an adhesive agent to level | step difference MEA. It is explanatory drawing at the time of joining the resin frame member to the said level | step difference MEA in the manufacturing method of the said comparative example. In a 2nd manufacturing method, it is explanatory drawing at the time of applying an adhesive agent to level | step difference MEA. It is explanatory drawing at the time of joining a resin frame member to the said level | step difference MEA in the said 2nd manufacturing method. It is explanatory drawing of the relationship between a joining area | region and peeling durability. It is principal part cross-sectional explanatory drawing of other MEA with a resin frame.

  As shown in FIGS. 1 and 2, an MEA (electrolyte membrane / electrode structure) 10 with a resin frame to which the manufacturing method of the present invention is applied is a horizontally long (or vertically long) rectangular polymer electrolyte power generation cell ( (Fuel cell) 12. 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 a fuel cell stack. The fuel cell stack is mounted on, for example, a fuel cell electric vehicle (not shown) as an in-vehicle fuel cell stack.

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

  The MEA 10 with a rectangular resin frame includes a step MEA 10a. As shown in FIG. 2, the step MEA 10a includes, for example, a solid polymer electrolyte membrane 18 that is a thin film of perfluorosulfonic acid containing moisture, and an anode electrode (first electrode) that sandwiches the solid polymer electrolyte membrane 18 20 and a cathode electrode (second electrode) 22. The solid polymer electrolyte membrane 18 is a cation exchange membrane, and an HC (hydrocarbon) electrolyte may be used in addition to the fluorine electrolyte.

  The cathode electrode 22 has a smaller planar dimension (outer dimension) than the solid polymer electrolyte membrane 18 and the anode electrode 20, and the solid polymer electrolyte membrane 18 and the anode electrode 20 have the same planar dimension. Instead of the above configuration, the anode electrode 20 may be configured to have a smaller planar dimension than the solid polymer electrolyte membrane 18 and the cathode electrode 22. At that time, the anode electrode 20 becomes the second electrode, and the cathode electrode 22 becomes the first electrode.

  As shown in FIG. 2, the anode electrode 20 includes a first electrode catalyst layer 20a bonded to one surface 18a of the solid polymer electrolyte membrane 18, and a first gas diffusion layer stacked on the first electrode catalyst layer 20a. Layer 20b. The first electrode catalyst layer 20a and the first gas diffusion layer 20b have the same planar dimensions (outer dimensions) and are set to the same (or less than the same) planar dimensions as the solid polymer electrolyte membrane 18. The first electrode catalyst layer 20a may be set to have a smaller planar dimension (or a larger planar dimension) than the first gas diffusion layer 20b.

  The cathode electrode 22 is provided with a second electrode catalyst layer 22a and a second gas diffusion layer 22b. The second electrode catalyst layer 22a is joined to the surface 18b of the solid polymer electrolyte membrane 18 with the outer peripheral surface 18be of the solid polymer electrolyte membrane 18 exposed. The second gas diffusion layer 22b is laminated on the second electrode catalyst layer 22a with the outer peripheral surface 22ae of the second electrode catalyst layer 22a exposed. The second electrode catalyst layer 22 a has a planar dimension larger than that of the second gas diffusion layer 22 b and is set to a planar dimension smaller than the planar dimension of the solid polymer electrolyte membrane 18.

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

  The first gas diffusion layer 20b is formed by a porous and conductive microporous layer 20b (m) and a carbon layer 20b (c) such as carbon paper or carbon cloth. The second gas diffusion layer 22b is formed by a porous and conductive microporous layer 22b (m) and a carbon layer 22b (c) such as carbon paper or carbon cloth. 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 solid polymer electrolyte membrane 18. Note that the microporous layers 20b (m) and 22b (m) may be provided as necessary, and may be unnecessary.

  The MEA 10 with a resin frame includes a film-like resin frame member (resin molded body or resin film) 24 having a uniform thickness on the entire surface joined to the outer peripheral surface 18be of the solid polymer electrolyte membrane 18. The inner peripheral end surface 24e of the resin frame member 24 and the outer peripheral end surface 22be of the second gas diffusion layer 22b of the cathode electrode 22 are separated from each other.

  The resin frame member 24 includes, 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, or the like.

  The resin frame member 24 is provided with an adhesive surface 24 a that is bonded to the outer peripheral surface 18 be of the solid polymer electrolyte membrane 18. Between the outer peripheral surface 18be of the solid polymer electrolyte membrane 18 and the adhesive surface 24a of the resin frame member 24, for example, an adhesive layer 26 made of an adhesive 26a such as a liquid fluorine elastomer is provided.

  Between the inner peripheral end surface 24e of the resin frame member 24 and the outer peripheral end surface 22be of the second gas diffusion layer 22b of the cathode electrode 22, there is an adhesive layer 26s formed on the second electrode catalyst layer 22a and made of an adhesive 26a. Provided. The adhesive layer 26 maintains the bonding strength between the step MEA 10a and the resin frame member 24, and the adhesive layer 26s prevents the second electrode catalyst layer 22a from coming into contact with the outside air. The adhesive layer 26 and the adhesive layer 26s may be connected.

  As shown in FIG. 1, one end edge of the power generation cell 12 in the direction of arrow B (horizontal direction in FIG. 1) communicates individually in the direction of arrow A, which is the stacking direction, and the oxidant gas inlet communication hole. 30a, a cooling medium inlet communication 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 in the direction of arrow B of the power generation cell 12 is individually communicated in the direction of arrow A, a fuel gas inlet communication hole 34a for supplying fuel gas, a cooling medium outlet communication hole 32b for discharging the cooling medium, And an oxidant gas outlet communication hole 30b for discharging the oxidant gas. 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.

  The outer peripheral end of the resin frame member 24 has an oxidant gas inlet communication hole 30a, a cooling medium inlet communication hole 32a, a fuel gas outlet communication hole 34b, a fuel gas inlet communication hole 34a, a cooling medium outlet communication hole 32b, and an oxidant gas outlet communication. Each communication hole is not formed at the inner side of the hole 30b.

  On the surface 16a of the cathode separator 16 facing the MEA 10 with the resin frame, a plurality of oxidant gas flow paths extending in the direction of arrow B are communicated with the oxidant gas inlet communication hole 30a and the oxidant gas outlet communication hole 30b. 36 is provided.

  A plurality of fuel gas flow paths 38 extending in the direction of arrow B are formed on the surface 14a of the anode separator 14 facing the MEA 10 with the resin frame, which communicates with the fuel gas inlet communication hole 34a and the fuel gas outlet communication hole 34b. Is done. Between the surface 14b of the anode separator 14 and the surface 16b of the cathode separator 16 which are adjacent to each other, a plurality of pieces extending in the direction of arrow B are communicated with the cooling medium inlet communication hole 32a and the cooling medium outlet communication hole 32b. A cooling medium flow path 40 is formed.

  As shown in FIGS. 1 and 2, the first seal member 42 is integrated with the surfaces 14 a and 14 b of the anode separator 14 around the outer peripheral end of the anode separator 14. The second seal member 44 is integrated with the surfaces 16 a and 16 b of the cathode separator 16 around the outer peripheral end of the cathode separator 16.

  As shown in FIG. 2, the first seal member 42 includes a first convex seal 42 a that contacts the resin frame member 24 constituting the MEA 10 with resin frame, and a second contact that contacts the second seal member 44 of the cathode separator 16. And a convex seal 42b. The first seal member 42 includes a third convex seal 42 c and a fourth convex seal 42 d that protrude on the opposite side of the resin frame member 24.

  The second seal member 44 constitutes a flat seal in which the surface that contacts the second convex seal 42b extends in a flat shape along the separator surface. Instead of the second convex seal 42b, the second seal member 44 may be provided with a convex seal (not shown).

  For the first seal member 42 and the second seal member 44, for example, EPDM, NBR, fluororubber, silicone rubber, fluorosilicone rubber, butyl rubber, natural rubber, styrene rubber, chloroprene or acrylic rubber or the like, cushion material Alternatively, an elastic seal member such as a packing material is used.

  Next, a manufacturing method according to the first embodiment of the present invention for manufacturing the MEA 10 with a resin frame will be described below.

  While the step MEA 10a is manufactured, the resin frame member 24 is prepared by cutting a film (for example, a PPS sheet) into a frame shape with a Thomson blade. In order to manufacture the step MEA 10a, first, a slurry made of a mixture of carbon black and PTFE (polytetrafluoroethylene) particles is applied to the flat surface of the carbon layer 20b (c) made of carbon paper, and dried. A microporous layer 20b (m), which is a formation, is formed.

  The first gas diffusion layer 20b is formed by bonding the carbon layer 20b (c) to the microporous layer 20b (m). Similarly, the microporous layer 22b (m) is formed, and the carbon layer 22b (c) is bonded to the microporous layer 22b (m), thereby forming the second gas diffusion layer 22b.

  On the other hand, after adding a solvent to the electrode catalyst, for example, a solution of a perfluoroalkylenesulfonic acid polymer compound is added as an ion conductive polymer binder solution. Then, an anode electrode ink and a cathode electrode ink are prepared by adding a solvent until a predetermined ink viscosity is reached.

  Therefore, as shown in FIG. 3, the anode electrode ink is applied to the PET film 50a by screen printing and dried by heating, whereby the anode electrode sheet 52 provided with the first electrode catalyst layer 20a is formed. The first electrode catalyst layer 20 a is set to have the same planar dimensions as the solid polymer electrolyte membrane 18.

  Similarly, the cathode electrode ink is applied to the PET film 50b by screen printing and dried by heating, whereby the cathode electrode sheet 54 provided with the second electrode catalyst layer 22a is formed. The second electrode catalyst layer 22 a is set to have a smaller planar dimension than the solid polymer electrolyte membrane 18.

  Next, hot pressing is performed in a state where the solid polymer electrolyte membrane 18 is sandwiched between the anode electrode sheet 52 and the cathode electrode sheet 54. Then, the PET films 50a and 50b are peeled to form a joined body (CCM) (catalyst coated membrane).

  Further, the first gas diffusion layer 20b and the second gas diffusion layer 22b sandwich the CCM between the microporous layers 20b (m) and 22b (m) and are integrated by hot pressing to produce the step MEA 10a. (See FIG. 2). At that time, on the surface 18b of the solid polymer electrolyte membrane 18, the outer peripheral surface 22ae of the second electrode catalyst layer 22a is exposed from the outer peripheral end of the second gas diffusion layer 22b, and the outer peripheral surface of the solid polymer electrolyte membrane 18 is exposed. 18be is exposed from the outer peripheral end of the second electrode catalyst layer 22a.

  As shown in FIG. 4, the step MEA 10a is arranged so that the cathode electrode 22 faces upward. The outer peripheral surface 22ae of the second electrode catalyst layer 22a is coated with two adhesive lines with a liquid adhesive 26aa and a liquid adhesive 26ab using a dispenser (not shown) over the entire periphery.

  The adhesive 26aa is applied along the first adhesive line with a predetermined width dimension h1 so as to be in contact with the outer peripheral end face 22be of the second gas diffusion layer 22b. The adhesive 26ab is applied along the second adhesive line with a predetermined width dimension h2 at a position close to the outer peripheral end of the second electrode catalyst layer 22a. The width h2 of the adhesive 26ab is set to a value larger than the width h1 of the adhesive 26aa (h1 <h2).

  Next, as shown in FIG. 5, the resin frame member 24 is disposed on the step MEA 10a, and is subjected to pressure and heat treatment by a servo press machine (not shown). Therefore, the adhesive 26aa flows between the inner peripheral end surface 24e of the resin frame member 24 and the outer peripheral end surface 22be of the cathode electrode 22, while the adhesive 26ab is solid from the outer peripheral end of the second electrode catalyst layer 22a. It flows on the outer peripheral surface 18be of the polymer electrolyte membrane 18. Accordingly, the adhesive 26aa is cured to form the adhesive layer 26s, and the adhesive 26ab is cured to form the adhesive layer 26, whereby the MEA 10 with a resin frame is manufactured (see FIG. 2).

  Therefore, a test piece obtained by cutting the MEA 10 with a resin frame into a strip shape was immersed in 90 ° C. water for 3000 hours, and then allowed to stand in an environment of 50% RH at 23 ° C. for 12 hours. Further, after the first gas diffusion layer 20b is peeled off, a test piece from which the second gas diffusion layer 22b is peeled is obtained, and the end of the resin frame member 24 and the end of the CCM are obtained by an autograph manufactured by Shimadzu Corporation. The peel strength of 180 ° was measured.

  On the other hand, as shown in FIG. 6, a comparison piece was created by the comparison step MEA 10 a (ref.). In the comparison piece, the adhesive 26a (ref.) Is applied on the outer peripheral surface 18be of the solid polymer electrolyte membrane 18 with a predetermined width dimension h2 over a region close to the outer peripheral end of the second electrode catalyst layer 22a. It was crafted. Other manufacturing steps are the same as those in the first embodiment. As a result, the peel strength of the test piece was 3 times or more higher than the peel strength of the comparative piece.

  Specifically, in the comparison piece, as shown in FIG. 6, the adhesive 26 a (ref.) Is applied on the outer peripheral surface 18 be of the solid polymer electrolyte membrane 18. For this reason, in the adhesive 26a (ref.), The reaction of the contact portion with the outer peripheral surface 18be gradually proceeds, and the reaction region 56 is generated.

  Next, as shown in FIG. 7, when the resin frame member 24 is pressed and heated on the step MEA 10 a (ref.), The adhesive 26 a (ref.) Is applied on the outer peripheral surface 18 be of the solid polymer electrolyte membrane 18. It is being spread out. At this time, the flowing adhesive 26a (ref.) And the reaction region 56 are clearly separated, and a clear interface 58 may be formed between them. Accordingly, when the adhesive 26a (ref.) Is pressurized and heated to be cured and the adhesive layer 26 is formed, the adhesive layer 26 is easily peeled off at the interface 58, and the adhesive strength is reduced. .

  On the other hand, in the first embodiment, as shown in FIG. 4, when the step MEA 10a and the resin frame member 24 are joined by the adhesive 26ab, the adhesive 26ab is used as the outer periphery of the second electrode catalyst layer 22a. It is applied to the surface 22ae. Thereby, the time for the adhesive 26ab and the solid polymer electrolyte membrane 18 to contact each other can be shortened as much as possible, and the variation in the adhesive quality can be reduced. For this reason, the effect that the step MEA 10a and the resin frame member 24 can be firmly and reliably bonded by a simple process is obtained.

  Next, operation | movement of the electric power generation cell 12 comprised in this way is demonstrated below.

  First, 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. Supplied. 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 cathode separator 16, moves in the direction of arrow B, and is supplied to the cathode electrode 22 of the step MEA 10a. On the other hand, the fuel gas is introduced into the fuel gas flow path 38 of the anode 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 step MEA 10a.

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

  Next, 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 32 a is introduced into the cooling medium flow path 40 between the anode separator 14 and the cathode 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 step MEA 10a.

  Next, the manufacturing method which concerns on the 2nd Embodiment of this invention for manufacturing MEA10 with a resin frame is demonstrated below. In addition, in 2nd Embodiment, it manufactures similarly to said 1st Embodiment, The detailed description is abbreviate | omitted about the same process.

  As shown in FIG. 8, on the outer peripheral surface 22ae of the second electrode catalyst layer 22a, the two adhesive lines are applied with the liquid adhesive 26aa and the liquid adhesive 26ac by using a dispenser (not shown) over the entire periphery. Work is performed.

  The adhesive 26ac is applied along the second adhesive line with a predetermined width dimension h3 (h1 <h3) from the outer peripheral surface 22ae of the second electrode catalyst layer 22a to the outer peripheral surface 18be of the solid polymer electrolyte membrane 18. Is done. At this time, the adhesive area S1 applied to the outer peripheral surface 18be of the solid polymer electrolyte membrane 18 is an adhesive area S2 between the solid polymer electrolyte membrane 18 and the resin frame member 24 on the outer peripheral surface 18be (see FIG. 9). Of 60% or less.

  Furthermore, as shown in FIG. 9, the resin frame member 24 and the step MEA 10a are subjected to pressure and heat treatment. Therefore, the adhesive 26aa flows between the inner peripheral end surface 24e of the resin frame member 24 and the outer peripheral end surface 22be of the cathode electrode 22, while the adhesive 26ac is on the outer peripheral surface 18be of the solid polymer electrolyte membrane 18. It flows toward the outer edge.

  In this case, a part of the adhesive 26ac (adhesive area S1) is previously coated on the outer peripheral surface 18be of the solid polymer electrolyte membrane 18, and the reaction region 56 is generated as time passes. . Accordingly, an interface 58 is formed between the flowing adhesive 26ac and the reaction region 56 when the adhesive 26ac is spread on the outer peripheral surface 18be of the solid polymer electrolyte membrane 18.

  Here, in the second embodiment, the adhesive area S1 applied in advance to the outer peripheral surface 18be of the solid polymer electrolyte membrane 18 is set to 60% or less of the adhesive area S2 on the outer peripheral surface 18be. Thereby, the solid polymer electrolyte membrane 18 and the resin frame member 24 can maintain a bonding region having a high bonding strength that is 40% or more of the bonding area S2, and favorably suppress the peeling of the adhesive layer 26. Is possible.

  FIG. 10 shows the relationship between the bonding region {(bonding area S2−bonding area S1) / bonding area S2} × 100% of the adhesive layer 26 and the peeling durability. The peeling durability is the ratio of the peel strength in each bonding region when the peel strength in the case where the bonding region is 100% is 100.

  As shown in FIG. 10, when the bonding region is 40% or more, that is, when the adhesive area S1 is 60% or less of the bonding area S2, good peel strength can be maintained. For this reason, the effect similar to said 1st Embodiment is acquired, such as being able to adhere | attach the level | step difference MEA10a and the resin frame member 24 firmly and reliably by a simple process.

  FIG. 11 is a cross-sectional explanatory view of a main part of another MEA (electrolyte membrane / electrode structure) 80 with a resin frame to which the manufacturing method of the present invention is applied. The same components as those of the resin framed MEA 10 are denoted by the same reference numerals, and detailed description thereof is omitted.

  The MEA 80 with a resin frame includes a step MEA 80 a and a resin frame member 82, and the step MEA 80 a and the resin frame member 82 are joined by an adhesive layer 26.

  The resin frame member 82 has a rectangular frame shape and is provided with an outer peripheral portion 82a having a thickness substantially equal to the thickness of the step MEA 80a (dimension in the direction of arrow A). The outer peripheral portion 82a is provided with an inner bulging portion 82b formed in a thin shape that bulges from the inner peripheral base end portion 82s to the cathode electrode 22 side via a stepped portion. The inner bulging portion 82b extends inward from the inner peripheral base end portion 82s with a predetermined length, and is disposed so as to cover the outer peripheral surface 18be of the solid polymer electrolyte membrane 18.

  The MEA 80 with a resin frame configured as described above is manufactured by the manufacturing method according to the first and second embodiments. Therefore, the same effect as when the MEA 10 with a resin frame is used can be obtained.

10, 80 ... MEA with resin frame 10a, 80a ... Step MEA
DESCRIPTION OF SYMBOLS 12 ... Power generation cell 14, 16 ... Separator 18 ... Solid polymer electrolyte membrane 18be ... Outer peripheral surface 20 ... Anode electrode 20a, 22a ... Electrode catalyst layer 20b, 22b ... Gas diffusion layer 22 ... Cathode electrode 24, 82 ... Resin frame member 24a ... Adhesive surface 26, 26s ... Adhesive layer 26a ... Adhesive 30a ... Oxidant gas inlet communication hole 30b ... Oxidant gas outlet communication hole 32a ... Cooling medium inlet communication hole 32b ... Cooling medium outlet communication hole 34a ... Fuel gas inlet communication Hole 34b ... Fuel gas outlet communication hole 36 ... Oxidant gas flow path 38 ... Fuel gas flow path 40 ... Cooling medium flow path 42, 44 ... Seal member

Claims (3)

A first electrode is provided on one surface of the solid polymer electrolyte membrane, a second electrode is provided on the other surface of the solid polymer electrolyte membrane, and the planar dimensions of the first electrode are The second electrode is set to a size larger than the planar size of the second electrode, and the second electrode has a catalyst layer provided on the other surface with the outer peripheral surface of the solid polymer electrolyte membrane exposed, and the catalyst layer Step MEA provided with a gas diffusion layer provided on the catalyst layer in a state where the outer peripheral surface of the catalyst layer is exposed,
A resin frame member bonded to the outer peripheral surface of the solid polymer electrolyte membrane exposed to the outside of the second electrode;
A method for producing an MEA with a resin frame for a fuel cell, comprising:
The first electrode is provided on the one surface of the solid polymer electrolyte membrane, and the outer peripheral surface of the catalyst layer is formed on the other surface of the solid polymer electrolyte membrane from an outer peripheral end of the gas diffusion layer. A step of manufacturing the step MEA by projecting and providing the second electrode;
Forming the resin frame member;
Applying an adhesive to the outer peripheral surface of the catalyst layer;
A step of joining the step MEA and the resin frame member by overlapping the step MEA and the resin frame member, pressurizing and heating;
The manufacturing method of MEA with a resin frame characterized by having.   The manufacturing method according to claim 1, wherein the adhesive is disposed on the catalyst layer in contact with an outer peripheral end surface of the gas diffusion layer, and on the catalyst layer, an outer periphery of the catalyst layer. A method for producing an MEA with a resin frame, which is applied to a second adhesive line arranged at an end.   The manufacturing method according to claim 1, wherein the adhesive is applied from the outer peripheral surface of the catalyst layer to an exposed portion of the solid polymer electrolyte membrane, and the exposure of the solid polymer electrolyte membrane is performed. The method for producing an MEA with a resin frame, wherein an adhesive area applied to the part is set to 60% or less of an adhesive area in the exposed part.

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