JP6229874B2 - Membrane electrode assembly with frame, single fuel cell and fuel cell stack - Google Patents

Description

  The present invention relates to a membrane electrode assembly with a frame, a fuel cell single cell, and a fuel cell stack. In particular, the present invention relates to a polymer electrolyte fuel cell.

  Conventionally, an electrolyte with a fuel frame for a fuel cell that can be joined to a resin frame member firmly and easily around an outer periphery of a solid polymer electrolyte membrane constituting a step electrolyte membrane / electrode structure by a simple process A method of manufacturing a membrane / electrode structure has been proposed (see Patent Document 1).

  In this method of manufacturing an electrolyte membrane / electrode structure with a resin frame for a fuel cell, a first electrode having a first catalyst layer and a first gas diffusion layer is disposed on one surface of a solid polymer electrolyte membrane, and A second electrode having a second catalyst layer and a second gas diffusion layer is disposed on the other surface of the solid polymer electrolyte membrane, and the plane dimension of the first gas diffusion layer is the plane of the second gas diffusion layer. An electrolyte membrane / electrode structure set to a size larger than the size, a thin-walled inner peripheral projection that circulates around the outer periphery of the solid polymer electrolyte membrane and protrudes toward the second gas diffusion layer, and an inner peripheral projection And a resin frame member provided with an inner wall facing the outer peripheral end of the first gas diffusion layer, and a manufacturing method of an electrolyte membrane / electrode structure with a resin frame for a fuel cell It is. Then, the method of manufacturing the electrolyte membrane / electrode structure with a resin frame for a fuel cell is configured such that the solid polymer electrolyte membrane and the inner peripheral projection of the resin frame member are bonded around the outer periphery of the second gas diffusion layer. A first step of bonding by a layer, and the first step is a step of applying a first adhesive on the inner peripheral protrusion of the resin frame member in the vicinity of the inner wall portion; and After the first adhesive is semi-cured, the second adhesive is applied to the inner peripheral protrusion in a range other than the application range of the first adhesive, and the solid polymer electrolyte is formed by the first adhesive and the second adhesive. A step of joining the outer peripheral edge of the film and the inner peripheral protrusion of the resin frame member. Further, as a preferred embodiment of the method of manufacturing the electrolyte membrane / electrode structure with a resin frame for a fuel cell, the outer peripheral end portion of the first gas diffusion layer and the inner wall portion of the resin frame member are joined by a resin impregnated portion. A manufacturing method having a second step is described.

JP 2013-131417 A

  However, in the method for producing an electrolyte membrane / electrode structure with a resin frame for a fuel cell described in Patent Document 1, the outer peripheral end of the first gas diffusion layer and the inner wall of the resin frame member are made of resin. Since it has the 2nd process joined by an impregnation part, processing time of the process was long and there was a problem in mass productivity.

  In addition, in the electrolyte membrane / electrode structure with a resin frame for a fuel cell produced by the manufacturing method described in Patent Document 1, when the membrane electrode assembly and the frame are joined, the function of positioning them Is not provided, and there is a problem in productivity because the joining position varies when assembled.

  Furthermore, in an electrolyte membrane / electrode structure with a resin frame for a fuel cell produced by the manufacturing method described in Patent Document 1, a membrane electrode to which a fluorine-based polymer is generally applied when not joined by a resin-impregnated portion By simply joining the joined body and the frame using an adhesive, it is not possible to generate a chemical adhesive force against a chemically stable fluoropolymer, for example, during operation of a fuel cell. Depending on the high demand for environmental changes such as pressure change and temperature / humidity change, the bonded membrane electrode assembly and the frame may be separated.

  The present invention has been made in view of the above-described problems of the prior art. The present invention provides a membrane electrode assembly with a frame, a fuel cell single cell, and a fuel cell stack that are excellent in mass productivity and productivity, and that can sufficiently ensure the bonding strength between the membrane electrode assembly and the frame. Objective.

  The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, a part of the outer peripheral edge part of both surfaces of the predetermined electrolyte membrane is opposed to the inner peripheral edge part of the predetermined first resin frame and the inner peripheral edge part through a bonding layer made of an adhesive or an adhesive. It has been found that the above object can be achieved by, for example, a structure having a structure sandwiched by the predetermined second resin frame, and the present invention has been completed.

That is, the frame with the membrane electrode assembly of the present invention includes a membrane electrode assembly sandwiched between the electrolyte membrane a pair of electrode layers, the membrane electrode assembly is disposed on the electrode layer side of the hand of the membrane electrode assembly a first resin frame having an opening to place the body and a plurality of manifold holes, is disposed on the electrode layer side of the other side of the membrane electrode assembly opening for placing the membrane electrode assembly possess a second resin frame disposed to face the inner peripheral edge portion of the first resin frame, the inner peripheral edge portion and the second resin frame of the first resin frame outer peripheral edge portion of the conductive Kaishitsu film a bonding layer made of adhesive or pressure-sensitive adhesive bonded to, the the protrusions formed on at least one of the inner peripheral edge portion and the second resin frame of the first resin frame, the protrusions are inserted in the first inner peripheral edge portion and the second resin frame of the resin frame And a hole formed in the outer peripheral portion of the other及 beauty the electrolyte membrane, the electrolyte membrane outer periphery of the inner peripheral edge portion and the inner peripheral portion opposing the second of the first resin frame It is characterized by being sandwiched and fixed between resin frames .

  Moreover, the fuel cell single cell of this invention is provided with the membrane electrode assembly with a flame | frame of the said invention, and a pair of separator which clamps the membrane electrode assembly with a flame | frame.

  Furthermore, the fuel cell stack of the present invention has a structure in which a plurality of the single fuel cell of the present invention is stacked.

According to the present invention, an opening placing the membrane electrode assembly is sandwiched between the electrolyte membrane a pair of electrode layers disposed on the electrode layer side of the hand of the membrane electrode assembly the membrane electrode assembly a first resin frame having a plurality of manifold holes, is disposed on the electrode layer side of the other side of the membrane electrode assembly have a opening for placing the membrane electrode assembly of the first resin frame a second resin frame disposed to face the inner peripheral edge portion, the electrostatic Kaishitsu joining outer peripheral edges of the membrane to the inner peripheral edge portion and the second resin frame of the first resin frame adhesive or a bonding layer comprising a material, said a protrusion formed on at least one of the inner peripheral edge portion and the second resin frame of the first resin frame, an inner peripheral edge portion of the first resin frame the protrusions are inserted and the outer peripheral edge of the other及 beauty the electrolyte film of the second resin frame And a hole formed in, configuration of the outer peripheral edge of the electrolyte membrane was fixed by pinching between the second resin frame opposed to the inner peripheral edge portion and the inner periphery of the first resin frame It was made. Therefore, it is excellent in mass productivity and productivity, and it is difficult for the membrane electrode structure to be pulled out by the structure in which the projection and the hole are fitted, and the membrane electrode junction with the frame can sufficiently secure the bonding strength between the membrane electrode assembly and the frame. Bodies, fuel cell single cells and fuel cell stacks can be provided.

FIG. 1 is a perspective view (A) illustrating a fuel cell stack according to the first embodiment of the present invention and a perspective view (B) in an exploded state. FIG. 2 is an exploded perspective view illustrating a single fuel cell constituting the fuel cell stack shown in FIG. FIG. 3 is a perspective view for explaining a membrane electrode assembly with a frame constituting the single fuel cell shown in FIG. 4 is an exploded perspective view for explaining the membrane electrode assembly with a frame constituting the single fuel cell shown in FIG. 1 and an enlarged perspective view for explaining the main part thereof. FIG. 5 is an enlarged perspective view illustrating a main part of a membrane electrode assembly with a frame constituting a single fuel cell of a fuel cell stack according to a second embodiment of the present invention. FIG. 6 is a top view (A) and an enlarged view (B) for explaining a main part of a membrane electrode assembly with a frame constituting a fuel cell unit cell of a fuel cell stack according to a third embodiment of the present invention. is there. FIG. 7 is a top view (A) illustrating an essential part of a membrane electrode assembly with a frame constituting a fuel cell single cell of a fuel cell stack according to a fourth embodiment of the present invention, and an enlarged view (B) thereof. is there. FIG. 8: is the top view (A) explaining the principal part of the membrane electrode assembly with a frame which comprises the fuel cell single cell of the fuel cell stack concerning the 5th Embodiment of this invention, and its enlarged view (B) is there. FIG. 9 is a top view (A) illustrating an essential part of a membrane electrode assembly with a frame constituting a fuel cell single cell of a fuel cell stack according to a sixth embodiment of the present invention, and an enlarged view (B) thereof. is there. FIG. 10 is a cross-sectional view illustrating a main part of a fuel cell single cell of a fuel cell stack according to a seventh embodiment of the present invention. FIG. 11 is a plan view (A) illustrating a main part of a membrane electrode assembly with a frame constituting a fuel cell single cell of a fuel cell stack according to an eighth embodiment of the present invention, and A- in FIG. It is sectional drawing (B) along the A line. 12 shows a membrane electrode assembly with a frame constituting a fuel cell single cell of a fuel cell stack according to a ninth embodiment of the present invention, with a frame surrounded by a line at the same position as the surrounding line Z in FIG. It is a perspective view explaining the principal part of a membrane electrode assembly.

  Hereinafter, a membrane electrode assembly with a frame, a fuel cell single cell, and a fuel cell stack according to an embodiment of the present invention will be described in detail with reference to the drawings. In addition, the dimension ratio of drawing quoted with the following forms is exaggerated on account of description, and may differ from an actual ratio.

(First embodiment)
FIG. 1 is a perspective view (A) illustrating a fuel cell stack according to the first embodiment of the present invention and a perspective view (B) in an exploded state. FIG. 2 is an exploded perspective view illustrating the single fuel cell constituting the fuel cell stack shown in FIG. FIG. 3 is a perspective view for explaining a membrane electrode assembly with a frame constituting the single fuel cell shown in FIG. FIG. 4 is an exploded perspective view (A) for explaining the membrane electrode assembly with a frame constituting the fuel cell single cell shown in FIG. 1 and an enlarged perspective view (B) for explaining an essential part thereof.

  As shown in FIG. 1B, a fuel cell stack FS according to the first embodiment includes a plurality of fuel cell modules M in which a plurality of fuel cell single cells C are stacked and integrated, and the fuel cell modules M And a seal plate P interposed therebetween. The fuel cell single cell C and the seal plate P in the illustrated example are both rectangular plate shapes having substantially the same vertical and horizontal dimensions. In FIG. 1B, two fuel cell modules M and one seal plate P are shown, but in reality, more fuel cell modules M and seal plates P are stacked.

  In addition, the fuel cell stack FS has end plates 56A and 56B arranged at both ends in the stacking direction of the fuel cell module M, respectively, and a stacking end surface on the long side of the single fuel cell C (upper and lower surfaces in FIG. 1). In addition, fastening plates 57A and 57B are provided, and reinforcing plates 58A and 58B are provided on the laminated end surface on the short side. Each of the fastening plates 57A, 57B and the reinforcing plates 58A, 58B has a size extending over the entire length in the stacking direction of the stack A composed of the fuel cell module M and the seal plate P. Link.

  In this way, the fuel cell stack FS has a case-integrated structure as shown in FIG. 1A, and each fuel cell module M and the seal plate P are constrained and pressurized in the stacking direction to form individual fuel cell single cells. A predetermined contact surface pressure is applied to C, and the gas sealability, conductivity, etc. are maintained satisfactorily.

  As shown in FIG. 2, the fuel cell single cell C includes a membrane electrode assembly 1 with a frame and separators 6A and 6B. The separators 6A and 6B sandwich the membrane electrode assembly 1 with a frame. It has the structure. Note that a first resin frame 3 and separators 6A and 6B, which will be described later, each have a rectangular plate shape having substantially the same vertical and horizontal dimensions.

  Further, as shown in FIG. 2, the membrane electrode assembly 1 with a frame includes a membrane electrode assembly 2, a first resin frame 3, and a second resin frame 4. This membrane electrode assembly 2 is generally called MEA (Membrane Electrode Assembly), and has a structure in which an electrolyte membrane 21 made of a solid polymer is sandwiched between a pair of electrode layers (anode, cathode) 22. Yes. Further, the electrolyte membrane 21 has a structure in which the outer peripheral edge portions 2a on both sides are exposed. Further, the membrane electrode assembly 2 is supplied with an anode gas (hydrogen-containing gas) at the anode and is supplied with a cathode gas (oxygen-containing gas / air) at the cathode to generate electric power by an electrochemical reaction. Although not shown, the membrane / electrode assembly includes those having a gas diffusion layer made of carbon paper or a porous body on the surfaces of the anode and the cathode.

  Each of the separators 6A and 6B is a metal plate member having an inverted shape, and is made of stainless steel, for example, and can be formed into an appropriate shape by pressing. Each separator 6A, 6B has a central portion corresponding to the membrane electrode assembly 2 formed in a wave shape in a cross section in the short side direction. This wave shape is continuous in the long side direction as shown in the figure.

  The framed membrane electrode assembly 1 and the separators 6A and 6B have three manifold holes H1 to H3 and H4 to H6, respectively, at both ends on the short side. The manifold holes H1 to H3 shown on the left side of FIGS. 1 to 3 are for cathode gas discharge (H1), cooling fluid discharge (H2), and anode gas supply (H3), and communicate with each other in the stacking direction. The respective flow paths are formed. Also, the manifold holes H4 to H6 shown on the right side of FIGS. 1 to 3 are for anode gas discharge (H4), for cooling fluid supply (H5) and for cathode gas supply (H6), and communicate with each other in the stacking direction. Thus, the respective flow paths are formed. The supply and discharge may be partially or entirely in a reverse positional relationship.

  The fuel cell single cell C forms a fuel cell module M by laminating a predetermined number. At this time, a flow path for cooling fluid (for example, water) is formed between adjacent fuel cell single cells C, and a flow path for cooling fluid is also formed between adjacent fuel cell modules M. . Therefore, the seal plate P is disposed between the fuel cell modules M, that is, in the flow path of the cooling fluid.

  The seal plate P is formed by molding a single conductive metal plate, is substantially the same rectangular plate shape as the above-described fuel cell single cell C and has the same size in plan view, and is formed on both short sides. Are formed with manifold holes H1 to H6 similar to those of the single fuel cell C. This seal plate P is provided with a seal member (not shown) around each of the manifold holes H1 to H6, and an outer peripheral seal member 51 and an inner peripheral seal member 52 are provided in parallel on the entire periphery thereof, The outer peripheral seal member 51 prevents rainwater and the like from entering from the outside, and the inner peripheral seal member 52 prevents leakage of the cooling fluid flowing through the flow path between the fuel cell modules M.

  Further, as shown in FIGS. 2 and 3, the first resin frame 3 and the second resin frame 4 have openings 3 a and 4 a, and the first resin frame 3 and the second resin frame 4 are provided. The resin frame 4 is disposed around the membrane electrode assembly 2 and on one side and the other side of the pair of electrode layers. In this way, the membrane electrode assembly 2 is disposed in the openings 3 a and 4 a of the first resin frame 3 and the second resin frame 4.

  As shown in FIGS. 2 and 3, the second resin frame 4 has the same size and shape as the inner peripheral edge 3 b of the first resin frame 3. The second resin frame 4 is preferably integral as shown in the illustrated example. However, it is not limited to this, and although not shown, it may be a separate body. The exposed outer peripheral edge 2a of the electrolyte membrane 21 is sandwiched between the inner peripheral edge 3b of the first resin frame 3 and the second resin frame 4 via the bonding layers 5A and 5B. Here, the bonding layers 5A and 5B are made of an adhesive or a pressure-sensitive adhesive. The bonding layers 5A and 5B may be integrally formed as in the illustrated example, or may be formed separately (not shown).

  As shown in FIGS. 2 and 3, the seal member S is continuously arranged around the peripheral edge of the first resin frame 3 and the separators 6 </ b> A and 6 </ b> B and the manifold holes H <b> 1 to H <b> 6. . These seal members S also function as an adhesive, and airtightly join the membrane electrode assembly 1 with the frame and the separators 6A and 6B. Further, the seal member S disposed around the manifold holes H1 to H6 has an opening at a corresponding portion in order to supply fluid according to each layer while maintaining the airtightness of each manifold.

  Furthermore, as shown in FIG. 4, either one or both of the inner peripheral edge 3 b of the first resin frame 3 and the second resin frame 4 are provided with protrusions 3 d, 4 d, the inner peripheral edge of the first resin frame 3. The other or both of 3b and the second resin frame 4, and the outer peripheral edge 2a of the electrolyte membrane 21 have holes 3c, 4c, and 2c. In the assembled state, the projections 3d and 4d are fitted in the holes 3c, 4c and 2c. In the figure, 21 indicates an electrolyte membrane, and 22 indicates an electrode layer (in the illustrated example, the upper side is a cathode and the lower side is an anode). Moreover, a hole and a processus | protrusion can be formed by conventionally well-known injection molding, press molding, machining, etc., for example. Further, for example, when a minute burr is generated by press forming or machining, the bonding strength between the electrolyte membrane and the resin frame can be increased by arranging the burr on the bonding layer side.

  The configuration of the present embodiment can also be applied when the anode and the cathode are interchanged. However, compared to the cathode side in environmental changes such as changes in operating pressure and temperature and humidity during the operation of the fuel cell. Since the anode side is often set to a high pressure, in consideration of the stress concentration on the first resin frame, it is preferable to arrange the second resin frame on the cathode side as shown in the figure.

  In this manner, the exposed outer peripheral edge of the electrolyte membrane is sandwiched between the inner peripheral edge of the first resin frame and the second resin frame facing the inner peripheral edge via a bonding layer made of an adhesive or an adhesive. The projections of one or both of the first resin frame and the second resin frame, the holes of either one or both of the first resin frame and the second resin frame, and the electrolyte membrane With the structure in which the projections are fitted in the holes, the membrane electrode structure is excellent in mass productivity and productivity, and the membrane electrode structure is difficult to be pulled out by the structure in which the projections and the holes are fitted. It is possible to provide a membrane electrode assembly with a frame, a fuel cell single cell, and a fuel cell stack that can sufficiently secure the bonding strength between the body and the frame. In addition, because the productivity is good and it is difficult for variations in the joining position to occur during assembly, it is possible to suppress the increase in leakage between the electrodes when the variation in the bonding area occurs, and the frame in which various performance degradations such as performance degradation are suppressed. A membrane electrode assembly, a fuel cell single cell, and a fuel cell stack can be provided.

(Second Embodiment)
FIG. 5 is an enlarged perspective view illustrating a main part of a membrane electrode assembly with a frame constituting a single fuel cell of a fuel cell stack according to a second embodiment of the present invention. In the present embodiment, the same components as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Other configurations not shown in the figure are the same as those in the first embodiment, and detailed description thereof is omitted. As shown in FIG. 5, in this embodiment, the inner peripheral edge 3b of the first resin frame 3 has a protrusion 3d, and the outer peripheral edge 2a of the second resin frame 4 and the electrolyte membrane 21 is formed with holes 4c, The configuration of having 2c is different from the first embodiment. Although not shown, the configuration of the present embodiment can be employed even when the anode and the cathode are interchanged.

  With such a configuration, in the manufacturing process, the holes of the electrolyte membrane and the second resin frame are usually fitted to the protrusions of the first resin frame disposed on the lower side from the viewpoint of handling. Therefore, positioning is easy. As a result, it is excellent in mass productivity and productivity, and the bonding strength between the membrane electrode assembly and the frame can be sufficiently secured.

(Third embodiment)
FIG. 6 is a top view (A) and an enlarged view (B) for explaining a main part of a membrane electrode assembly with a frame constituting a fuel cell unit cell of a fuel cell stack according to a third embodiment of the present invention. is there. In the present embodiment, the same components as those in the first or second embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Other configurations not shown in the figure are the same as those in the first or second embodiment, and thus detailed description thereof is omitted. As shown in FIG. 6, in the present embodiment, the protrusions 3d are arranged on the inner peripheral edge 3b of the first resin frame 3 with a uniform interval along the peripheral edge of the opening 3a. The configuration in which the second resin frame 4 is fitted in the hole 4c is different from the first or second embodiment. Although not shown, the configuration of the present embodiment can be employed even when the anode and the cathode are interchanged.

  With such a configuration, the membrane electrode structure is more difficult to be pulled out by the structure in which the projections and the holes that are uniformly arranged on the whole are fitted. As a result, it is excellent in mass productivity and productivity, and the bonding strength between the membrane electrode assembly and the frame can be sufficiently secured.

(Fourth embodiment)
FIG. 7 is a top view (A) illustrating an essential part of a membrane electrode assembly with a frame constituting a fuel cell single cell of a fuel cell stack according to a fourth embodiment of the present invention, and an enlarged view (B) thereof. is there. In the present embodiment, the same components as those in any of the first to third embodiments are denoted by the same reference numerals, and detailed description thereof is omitted. Other configurations not shown in the figure are the same as those in any of the first to third embodiments, and thus detailed description thereof is omitted. As shown in FIG. 7, in the present embodiment, the entire planar shape of the protrusion 3d is a rectangle, and the protrusion 3d has a rectangular long side that is an opening of the inner peripheral edge 3b of the first resin frame 3. The structure of being arrange | positioned along the periphery of 3a is different from the 1st-3rd form. Although not shown, it is preferable that the rectangle has round corners from the viewpoint of stress relaxation when tensile stress is applied. Further, although not shown, some of the planar shapes of the protrusions can be different. Further, although not shown, the configuration of the present embodiment can be adopted even when the anode and the cathode are interchanged.

  By adopting such a configuration, the structure in which the projection and the hole having a large pressure receiving area with respect to the tension of the membrane electrode structure are fitted to each other is further difficult to be pulled out. As a result, it is excellent in mass productivity and productivity, and the bonding strength between the membrane electrode assembly and the frame can be sufficiently secured.

(Fifth embodiment)
FIG. 8: is the top view (A) explaining the principal part of the membrane electrode assembly with a frame which comprises the fuel cell single cell of the fuel cell stack concerning the 5th Embodiment of this invention, and its enlarged view (B) is there. In the present embodiment, the same components as those in any of the first to fourth embodiments are denoted by the same reference numerals, and detailed description thereof is omitted. Other configurations not shown in the drawing are the same as those in any of the first to fourth embodiments, and thus detailed description thereof is omitted. As shown in FIG. 8, in the present embodiment, the entire planar shape of the protrusion 3d is an ellipse, and the protrusion 3d has an elliptical major axis that is the opening of the inner peripheral edge 3b of the first resin frame 3. The configuration of being disposed along the periphery of the portion 3a is different from the first to fourth embodiments. Although not shown, some of the planar shapes of the protrusions may be different. Although not shown, the configuration of the present embodiment can be employed even when the anode and the cathode are interchanged.

  By adopting such a configuration, the structure in which the projection and the hole having a large pressure receiving area with respect to the tension of the membrane electrode structure are fitted to each other is further difficult to be pulled out. As a result, it is excellent in mass productivity and productivity, and the bonding strength between the membrane electrode assembly and the frame can be sufficiently secured.

(Sixth embodiment)
FIG. 9 is a top view (A) illustrating an essential part of a membrane electrode assembly with a frame constituting a fuel cell single cell of a fuel cell stack according to a sixth embodiment of the present invention, and an enlarged view (B) thereof. is there. In the present embodiment, the same components as those in any of the first to fifth embodiments are denoted by the same reference numerals, and detailed description thereof is omitted. Other configurations not shown are the same as those in any one of the first to fifth embodiments, and thus detailed description thereof is omitted. As shown in FIG. 9, in this embodiment, the planar shape of the projection 3d disposed at the corner of the inner peripheral edge 3b of the first resin frame 3 in the projection 3d is a sector shape. This is different from the first to fifth embodiments. Although not shown, it is needless to say that the desired effect can be obtained even if a projection having a fan-shaped planar shape is provided at the protruding corner of the second resin frame, and it is included in the scope of the present invention. . Although not shown, the configuration of the present embodiment can be employed even when the anode and the cathode are interchanged.

  By adopting such a configuration, the structure in which the projection and the hole having a large pressure receiving area with respect to the tension toward the center of the membrane electrode structure are fitted to each other is further difficult to be pulled out. As a result, it is excellent in mass productivity and productivity, and the bonding strength between the membrane electrode assembly and the frame can be sufficiently secured.

(Seventh embodiment)
FIG. 10 is a cross-sectional view illustrating a main part of a fuel cell single cell of a fuel cell stack according to a seventh embodiment of the present invention. In the present embodiment, the same components as those in any of the first to sixth embodiments are denoted by the same reference numerals, and detailed description thereof is omitted. Other configurations not shown are the same as those in any one of the first to sixth embodiments, and thus detailed description thereof is omitted. As shown in FIG. 10, in this embodiment, the protrusion 3d is disposed on the outer peripheral side from the position of the bonding layers 5A and 5B in the plane direction, and the hole 4c corresponding to the position where the protrusion 3d is disposed is formed. The thickness of both the inner peripheral edge 3b of the first resin frame 3 and the second resin frame 4 at the position where the bonding layers 5A and 5B are disposed is the inner peripheral edge of the first resin frame 3 at the position where the bonding layers 5A and 5B are disposed. The configuration of being thicker than both the portion 3b and the second resin frame 4 is different from the first to sixth embodiments. Although not shown, the thickness of the inner peripheral edge of the first resin frame 3 or the second resin frame at the position where the hole corresponding to the position where the protrusion is disposed is the position where the bonding layer is disposed. Needless to say, the desired effect can be obtained even when the thickness of the inner peripheral edge portion of the corresponding first resin frame 3 or the thickness of the second resin frame is larger than the range of the present invention. Although not shown, the configuration of the present embodiment can be adopted when the position of the anode and the cathode is either up or down.

  With such a configuration, the membrane electrode structure is hardly pulled out by the structure in which the protrusion and the hole are fitted. As a result, it is excellent in mass productivity and productivity, and the bonding strength between the membrane electrode assembly and the frame can be sufficiently secured. Further, since there is no need to reduce the bonding layer, it is possible to further suppress the interelectrode leakage. Furthermore, since the structure in which the protrusion and the hole are fitted at a position where the thickness of the resin frame is thick can be formed, the bonding strength can be further increased. In addition, when a separator structure that applies a load to the joint, such as a metal separator by press working, the joint may have a rib shape and both sides of the joint may have a groove shape. When the gas flows, the gas is not used for the reaction and is wasted, but the portion can be closed with the resin frame, and therefore, a useless gas flow can be suppressed.

(Eighth embodiment)
FIG. 11 is a plan view (A) illustrating a main part of a membrane electrode assembly with a frame constituting a fuel cell single cell of a fuel cell stack according to an eighth embodiment of the present invention, and A- in FIG. It is sectional drawing (B) along the A line (however, only the 2nd resin frame side is shown). In the present embodiment, the same components as those in any of the first to seventh embodiments are denoted by the same reference numerals, and detailed description thereof is omitted. Other configurations not shown in the figure are the same as those in any one of the first to seventh embodiments, and thus detailed description thereof is omitted. As shown in FIG. 11, in the present embodiment, the second resin frame 4 is provided with ribs 4e and the holes 4c are provided in the ribs 4e. It is different from the form. A protrusion 3d is fitted in the hole 4c. Although not shown, the configuration of the present embodiment can be adopted regardless of whether the position of the anode and the cathode is up or down, and the rib can be provided on both the anode side and the cathode side.

  With such a configuration, the membrane electrode structure is hardly pulled out by the structure in which the protrusion and the hole are fitted. As a result, it is excellent in mass productivity and productivity, and the bonding strength between the membrane electrode assembly and the frame can be sufficiently secured. Moreover, since the structure in which the protrusion and the hole are fitted at a position where the thickness of the resin frame is thick can be formed, the bonding strength can be further increased.

(Ninth embodiment)
12 shows a membrane electrode assembly with a frame constituting a fuel cell single cell of a fuel cell stack according to a ninth embodiment of the present invention, with a frame surrounded by a line at the same position as the surrounding line Z in FIG. It is a perspective view explaining the principal part of a membrane electrode assembly. In the present embodiment, the same components as those in any of the first to eighth embodiments are denoted by the same reference numerals, and detailed description thereof is omitted. Other configurations not shown in the figure are the same as those in any of the first to eighth embodiments, and thus detailed description thereof is omitted. As shown in FIG. 12, in this embodiment, the first resin frame 3 is formed along the periphery of the opening between the base 3f and the inner peripheral edge 3b of the resin frame, and the resin The configuration in which the step portion 3g corresponding to the thickness of the frame is provided and the inner peripheral edge portion 3b has a shape biased to one side surface of the resin frame by the step portion 3g is different from the first to eighth embodiments. doing. Although not shown, the configuration of the present embodiment can be adopted regardless of whether the position of the anode and the cathode is up or down.

  With such a configuration, the strength of the first resin frame can be improved. As a result, it is excellent in mass productivity and productivity, and the bonding strength between the membrane electrode assembly and the frame can be sufficiently secured. Moreover, since the structure in which the protrusion and the hole are fitted at a position where the thickness of the resin frame is thick can be formed, the bonding strength can be further increased.

  As mentioned above, although this invention was demonstrated by some embodiment, this invention is not limited to these, A various deformation | transformation is possible within the range of the summary of this invention.

  For example, the configurations described in the membrane electrode assembly with frame, the fuel cell single cell, and the fuel cell stack in each embodiment described above are not limited to each embodiment, for example, each embodiment described above in each embodiment. It is possible to make combinations other than the above, or to change details of the configuration.

FS Fuel cell stack M Fuel cell module C Fuel cell single cell P Seal plate A Laminate H1 to H6 Manifold hole S Seal member 1 Membrane electrode assembly 2 Frame electrode assembly 2a Outer peripheral edge 2c, 3c, 4c Hole 3 1st resin frame 3a, 4a Opening 3b Inner peripheral edge 3d, 4d Protrusion 4 Second resin frame 5A, 5B Bonding layer 6A, 6B Separator 21 Electrolyte layer 22 Electrode layer 51 Outer peripheral seal member 52 Inner peripheral seal member 56A, 56B End plate 57A, 57B Fastening plate 58A, 58B Reinforcement plate

Claims (11)

A membrane electrode assembly in which an electrolyte membrane is sandwiched between a pair of electrode layers;
A first resin frame having a plurality of manifold holes opening to place the membrane is disposed on the electrode layer side of the hand of the electrode assembly the membrane electrode assembly,
The is disposed to face the inner peripheral edge portion of the upper Symbol first resin frame have a opening to place the other side of the disposed electrode layer side the membrane electrode assembly of the membrane electrode assembly 2 Resin frame ,
A bonding layer made of an adhesive or an adhesive that bonds the outer peripheral edge of the electrolyte membrane to the inner peripheral edge of the first resin frame and the second resin frame ;
A protrusion formed on at least one of the inner peripheral edge of the first resin frame and the second resin frame ;
A hole in which the protrusions are formed on the outer peripheral edge portion of the other及 beauty the electrolyte membrane of the inner peripheral edge portion and the second resin frame of the inserted first resin frame
With
An outer peripheral edge portion of the electrolyte membrane is sandwiched and fixed between an inner peripheral edge portion of the first resin frame and the second resin frame opposite to the inner peripheral edge portion. Membrane electrode assembly. The inner peripheral edge of the first resin frame has a protrusion,
2. The membrane electrode assembly with frame according to claim 1, wherein outer peripheral edge portions of the second resin frame and the electrolyte membrane have holes.   The protrusions are disposed at one or both of the inner peripheral edge of the first resin frame and the second resin frame at a uniform interval along the peripheral edge of the opening. The membrane electrode assembly with a frame according to 1 or 2. The planar shape of a part or all of the protrusion is a rectangle,
In the projection, the long side of the rectangle is disposed along the peripheral edge of one or both of the inner peripheral edge of the first resin frame and the second resin frame. The membrane electrode assembly with a frame according to any one of claims 1 to 3. The planar shape of a part or all of the protrusion is an ellipse,
The protrusion is characterized in that the major axis of the ellipse is disposed along the periphery of one or both of the inner peripheral edge of the first resin frame and the second resin frame. The membrane electrode assembly with a frame according to any one of claims 1 to 3.   Of the projections, the planar shape of the projections arranged in one or both of the inner corner portion and the second corner portion of the first resin frame and / or the second resin frame is a sector shape. The membrane electrode assembly with a frame according to any one of claims 1 to 5, wherein the membrane electrode assembly has a frame structure. A part or all of the protrusions are arranged on the outer peripheral side from the position of the bonding layer in the planar direction,
The thickness of one or both of the inner peripheral edge portion of the first resin frame and the second resin frame at the position where the hole corresponding to the position where the protrusion is disposed is arranged. The frame according to any one of claims 1 to 6, wherein a thickness of one or both of an inner peripheral edge of the first resin frame and a second resin frame at a position where the first resin frame is located is larger. Membrane electrode assembly. Ribs are disposed on either or both of the inner peripheral edge of the first resin frame and the second resin frame,
The membrane electrode assembly with a frame according to any one of claims 1 to 7, wherein the protrusion or the hole is disposed in the rib. The first resin frame is formed along the periphery of the opening between the base of the resin frame and the inner peripheral edge, and has a step portion corresponding to the thickness of the resin frame. ,
The membrane electrode assembly with frame according to any one of claims 1 to 8, wherein the inner peripheral edge portion has a shape biased to one side surface of the resin frame by the stepped portion. A framed membrane electrode assembly according to any one of claims 1 to 9,
A fuel cell single cell comprising: a pair of separators that sandwich the membrane electrode assembly with frame.   11. A fuel cell stack having a structure in which a plurality of fuel cell single cells according to claim 10 are stacked.

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