JP4600500B2 - Manufacturing method of fuel cell - Google Patents

Description

  The present invention relates to a composite electrolyte membrane, a membrane electrode assembly, a fuel cell, and a method for producing them, and in particular, an electrolyte layer composed of a polyelectrolyte and a reinforcing layer in which a porous polymer material is impregnated with an electrolyte. The present invention relates to a composite electrolyte membrane, a membrane electrode assembly, a fuel cell, and a method for producing them.

  A polymer electrolyte fuel cell using an electrolyte membrane can be operated at a low temperature, and can be reduced in size and weight. Therefore, application to a moving body such as an automobile is being studied. In particular, fuel cell vehicles equipped with polymer electrolyte fuel cells are gaining social interest as ecological cars.

  As shown in FIG. 14, such a polymer electrolyte fuel cell includes a membrane electrode assembly (MEA) 95 as main components, and includes a fuel (hydrogen) gas passage and an air gas passage. One fuel cell 90 called a single cell is formed by being sandwiched between separators 96 and 96. In the membrane electrode assembly 95, an anode side electrode (anode catalyst layer) 93a is laminated on one side of an electrolyte membrane 91 which is an ion exchange membrane, and a cathode side electrode (cathode catalyst layer) 93b is laminated on the other side. In the structure, diffusion layers 94a and 94b are disposed in the anode catalyst layer 93a and the cathode catalyst layer 93b, respectively.

  By the way, the electrolyte membrane 91 includes a reinforcing layer made of a porous polymer material such as polytetrafluoroethylene (PTFE) in order to ensure the strength of the membrane, and the reinforcing layer is impregnated with an electrolyte. Yes. A composite type electrolyte membrane including such a reinforcing layer is manufactured, for example, by a cast film forming method as shown in FIG. 13A (see Patent Document 1).

  Specifically, first, while the backing sheet 81 is conveyed, an electrolyte prepared by mixing an electrolyte polymer and a solvent is applied to one surface of the backing sheet 81 and then dried. Next, a reinforcing sheet 82 made of a porous polymer material is disposed on the surface of the dried electrolyte layer. In this arrangement state, the electrolyte layer and the reinforcing sheet 81 are at least pressurized so that the porous polymer material is impregnated with the electrolyte from one surface of the reinforcing sheet 82. Furthermore, an electrolyte is applied to the other surface of the reinforcing sheet 82 and dried to provide at least a reinforcing layer made of a porous polymer material on the backing sheet 81 and an electrolyte impregnated in the reinforcing layer. In addition, the composite electrolyte membrane 91 can be manufactured.

  Further, as shown in FIG. 13B, the composite electrolyte membrane 91 manufactured in this way is formed by using, for example, an anode and a cathode catalyst layer 93a, 93b formed on a backing sheet 81 using a jig. Then, transfer is performed by heating and pressurizing, and further catalyst layers 93 a and 93 b are formed on the surface of the composite electrolyte membrane 91.

JP 2006-147257 A

  However, since the cast film formation method described above impregnates the electrolyte on one side and the other side of the reinforcing sheet in different steps, even if an electrolyte prepared by mixing the same electrolyte polymer and solvent is used, the composite type There may be variations in the film characteristics between the one surface side and the other surface side of the electrolyte membrane, and it may be difficult to obtain uniform characteristics.

  Moreover, since the process of apply | coating an electrolyte with respect to each surface and drying a solvent is included, it may be difficult to obtain the electrolyte membrane with a fixed film thickness with high precision. Furthermore, depending on the accuracy of the manufacturing equipment, the reinforcing sheet may be displaced from a desired location with respect to the applied electrolyte, and in particular, the displacement of the anode and cathode catalyst layers is likely to occur.

  As described above, when both sides of the electrolyte membrane cannot obtain uniform membrane characteristics, and when the accuracy of the thickness of the electrolyte membrane and the position of the catalyst layer does not satisfy the desired range, assembly failure at the time of cell production In addition, there may be variations in performance during fuel cell power generation.

  The present invention has been made in view of such problems, and an object of the present invention is to make the characteristics of the electrolyte in the membrane uniform and to manufacture with a stable dimensional accuracy. An object of the present invention is to provide an electrolyte membrane, a membrane electrode assembly, a fuel cell, and a method for producing them.

  In order to solve the above problems, a method for producing a composite electrolyte membrane according to the present invention includes heating an electrolyte sheet made of an electrolyte and a reinforcing sheet made of a porous polymer material, and laminating the electrolyte layer. And a step of forming the laminate including the reinforcing layer, a folding step of folding the laminate so that the surfaces of the laminate overlap, and heating the folded laminate until the electrolyte is dissolved, It includes at least an impregnation step of impregnating the reinforcing layer with an electrolyte and a hydrolysis step of hydrolyzing the electrolyte of the impregnated laminate.

  According to the method for manufacturing a composite electrolyte membrane according to the present invention, in the laminating step, the electrolyte sheet can be integrated with the reinforcing sheet to form a laminate including the reinforcing layer and the electrolyte layer. As long as a laminate is formed, the method for laminating the two sheets is not particularly limited, but it is preferable to heat and press at least the electrolyte sheet and impregnate part of one surface of the reinforcing sheet.

  Next, in the folding step, the laminated body is bent so that the surfaces of the laminated body overlap, that is, the surfaces on the reinforcing layer side or the surfaces on the electrolyte layer side overlap at least. For the folding of the laminate, it is preferable to join the surfaces to be contacted by bending by heating and pressing. In addition, it is preferable that the laminate is folded in half around the central axis. However, if the electrolyte on both sides of the electrolyte membrane becomes homogeneous after the folding process described later, the number of folding and the folding method are particularly limited. Is not to be done.

  Further, in the impregnation step, the folded laminate is heated at least until the electrolyte is melted to impregnate the porous reinforcing layer with the electrolyte. In the impregnation step, it is more preferable to heat and pressurize the laminate. As a result, the electrolyte of one electrolyte sheet at the time of lamination is disposed on both surfaces of the laminate. And in a hydrolysis process, an ion exchange function can be provided to an electrolyte by hydrolyzing the electrolyte impregnated in the layered product.

  Such a composite electrolyte membrane manufacturing method eliminates the need to align the three sheets so that the electrolyte sheet is sandwiched between both sides of the reinforcing sheet, thus improving the alignment accuracy and improving the quality of the electrolyte membrane. Is stable. In addition, since the laminate is folded and impregnated with the electrolyte of one electrolyte sheet, a homogeneous electrolyte can be disposed on both sides of the composite electrolyte membrane (electrolyte membrane). Stabilize. In this way, it is possible to make the characteristics of the electrolyte in the electrolyte membrane uniform, obtain a highly accurate electrolyte membrane, and stabilize the performance of the fuel cell.

  The “electrolyte sheet” and “reinforcing sheet” referred to in the present invention are not particularly limited in shape, film thickness, etc., as long as they can be folded after being laminated, and include concepts such as a film, a film, and the like. It is a waste. The “reinforcing sheet” means a sheet made of a porous polymer material for the purpose of reinforcing the electrolyte membrane, and the “reinforcing layer” means at least an electrolyte for the purpose of reinforcing the electrolyte membrane. It refers to a layer having the porous polymer material formed in the thickness direction of the membrane, and includes a layer in which the polymer material is impregnated with an electrolyte. Further, the “composite electrolyte membrane” refers to a layer including at least an electrolyte layer made of an electrolyte and a reinforcing layer in which a porous polymer material is impregnated with an electrolyte.

  As another aspect, in the method for manufacturing a composite electrolyte membrane according to the present invention, it is more preferable that the laminate is folded so that the surfaces on the electrolyte layer side overlap in the folding step. According to the present invention, in the folding step, the laminate is folded so that the surface on the electrolyte layer side overlaps and the reinforcing layer side becomes the surface of the electrolyte membrane. Therefore, in the impregnation step, near the surface in the thickness direction of the electrolyte membrane. A reinforcing layer can be disposed on the surface layer portion of. As a result, the creep performance of the electrolyte membrane during use of the fuel cell can be improved.

  In the method of manufacturing a composite electrolyte membrane according to the present invention, it is more preferable that the laminated body is bent so that the surface on the reinforcing layer side overlaps in the bending step. According to the present invention, in the folding step, the laminate is folded so that the surface on the reinforcing layer side overlaps and the electrolyte layer side becomes the surface of the electrolyte membrane. Therefore, in the impregnation step, the electrolyte layer is formed on the surface layer in the thickness direction. As a result, the position of the reinforcing layer is stabilized. As a result, in the fuel cell equipped with the electrolyte membrane, the surface electrolyte layer suppresses variations in water movement within the surface of the electrolyte membrane during power generation, and further improves the adhesion between the electrolyte layer and the catalyst layer. And can stabilize the performance.

  The electrolyte (precursor polymer) according to the present invention may be a molten polymer as long as it does not thermally deteriorate and can provide an ion exchange function after hydrolysis. A perfluoro proton exchange resin of a fluoroalkyl copolymer having an ether side chain and a perfluoroalkyl main chain is preferably used. For example, Nafion (trade name) manufactured by DuPont, Aciplex (trade name) manufactured by Asahi Kasei, Flemion (trade name) manufactured by Asahi Glass, Gore-Select (trade name) manufactured by Japan Gore-Tex, etc. are exemplified. Examples thereof include a polymer of trifluorostyrene sulfonic acid and a product obtained by introducing a sulfonic acid group into polyvinylidene fluoride. Further, there are styrene-divinylbenzene copolymer, polyimide resin, etc., which are hydrocarbon proton exchange resins, in which sulfonic acid groups are introduced. These should be appropriately selected according to the use and environment in which the fuel cell is used, but a perfluoro type is preferable from the viewpoint of the life of the fuel cell.

  As the reinforcing sheet, it is necessary that the reinforcing sheet does not dissolve during the impregnation of the electrolyte. In particular, a water-repellent polymer is preferably included. The reinforcing sheet containing the water-repellent polymer is effective because the condensation and retention of water in the polymer electrolyte fuel cell hinders the supply of the electrode reactant. In particular, fluororesins such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) are preferably used because they have high water repellency. It is done. In addition, non-fluorine films such as polyethylene terephthalate, polyethylene, polypropylene, and polyimide can also be used.

  Further, in the method for manufacturing a composite electrolyte membrane according to the present invention, as described above, in the bending step, when the laminate is folded so that the surface on the reinforcing layer side overlaps, the lamination step is performed. In this, it is preferable to dispose at least one of a radical inhibitor or a water retention material that decomposes hydrogen peroxide into water and oxygen to suppress the generation of hydroxy radicals on the surface of the reinforcing layer after forming the laminate. preferable.

  As another aspect, in the laminating step, a radical inhibitor or a water retaining material that suppresses generation of hydroxy radicals by decomposing hydrogen peroxide into water and oxygen between the electrolyte sheet and the reinforcing sheet. You may arrange | position at least one of these.

  According to the present invention, the additive is added to the electrolyte at the center in the thickness direction of the electrolyte membrane in the impregnation step by sandwiching at least one additive of the radical inhibitor or the water retention material in the bending step. Can be fixed.

  As a result, when the fuel cell generates power, it is possible to prevent the additive from moving or being lost due to water movement. In the hydrolysis step, when water is transferred in the electrolyte membrane, when a radical inhibitor is disposed, hydrogen peroxide generated as a by-product during the power generation of the fuel cell is converted into water and oxygen. It is possible to suppress the generation of hydroxy radicals by being decomposed into, and to stably suppress the deterioration of the electrolyte membrane. On the other hand, when a water retention material is disposed, water retention and diffusion effects can be obtained, and a decrease in fuel cell performance due to deterioration in proton conductivity can be stably suppressed.

  The radical suppressing material referred to in the present invention refers to a “material for suppressing the generation of hydroxy radicals by decomposing hydrogen peroxide generated as a by-product into water and oxygen during power generation of the fuel cell”, For example, oxides of transition metals such as cerium, ruthenium, silver, tungsten, palladium, rhodium, zirconium, yttrium, manganese, molybdenum, lead, vanadium, and titanium can be given. The water-retaining material is not particularly limited as long as it can absorb water. For example, a water-absorbing polymer material such as polystyrene sulfonic acid or cellulose, or a water-absorbing inorganic material such as silica or titania. , Etc. may be mentioned.

  Such radical inhibitor and water retention material can be uniformly disposed on the surface of the reinforcing layer by physical vapor deposition (PVD) such as coating by die coating or spraying, sputtering, etc., and bending as described above. The sandwiching method is not particularly limited as long as the radical suppressing material and the water retaining material can be sandwiched between the reinforcing layers to the extent that they are not detached when bent.

  In addition, when a particulate material is used as the radical suppressing material and the water retention material, the particle size of the particulate material is more preferably larger than the porous pore diameter formed in the reinforcing sheet. By setting it as such a particle size, these particle materials can be suitably pinched | interposed at the time of a bending process.

  Moreover, the manufacturing method of the membrane electrode assembly (MEA) of a fuel cell is also disclosed as this invention. The method for producing a membrane electrode assembly according to the present invention is a method for producing a membrane electrode assembly for a fuel cell including a method for producing a composite electrolyte membrane, wherein the electrolyte after forming the laminate in the laminating step. An anode catalyst layer and a cathode catalyst layer are disposed on the surface of the layer, and in the bending step, the anode catalyst layer is disposed on one surface of the laminate, and the cathode catalyst layer is disposed on the other surface of the laminate. The laminated body is bent so as to be disposed at the bottom.

  According to the method for manufacturing a membrane / electrode assembly according to the present invention, the anode catalyst layer and the cathode catalyst layer are formed on the same surface on which the electrolyte layer of the laminate after the lamination step is formed. Can be arranged. As a result, if the accuracy of the folding position of the laminate can be maintained in the folding step, the positional relationship between the anode catalyst layer and the cathode catalyst layer can be prevented from shifting. And the diffusion layer mentioned above can be arrange | positioned after catalyst layer formation. By using the membrane electrode assembly manufactured in this way, it is possible to suppress poor assembly when the fuel cell is assembled, and variations in performance of the fuel cell during power generation.

  Another preferred embodiment of the method for producing a membrane / electrode assembly (MEA) is a method for producing a membrane / electrode assembly including the method for producing a composite electrolyte membrane, wherein in the lamination step, the laminate is formed in a strip shape. The anode catalyst layer and the cathode catalyst layer are formed along the short direction of the laminate on the surface of the electrolyte layer after forming the laminate, and a plurality of the catalyst layers are formed along the longitudinal direction. The anode catalyst layer and the cathode catalyst layer are arranged so that the anode catalyst layer and the plurality of cathode catalyst layers are alternately formed, and in the bending step, the anode catalyst layer is one of the laminates. More preferably, the laminate is bent along the longitudinal direction so that the cathode catalyst layer is disposed on the other surface of the laminate.

  According to the method for manufacturing a membrane / electrode assembly according to the present invention, the anode catalyst layer and the cathode catalyst layer are formed along the short direction in the same plane on which the electrolyte layer of the laminate after the lamination step is formed. These catalyst layers can be accurately arranged without misalignment so as to sandwich the composite electrolyte membrane. As a result, if the accuracy of the folding position of the laminate can be maintained in the folding step, the positional relationship between the anode catalyst layer and the cathode catalyst layer can be suppressed, and the assembly when assembled as a fuel cell is assembled. Defects and variations in performance during power generation of the fuel cell can be suppressed.

  In addition, since the anode catalyst layer and the cathode catalyst layer are arranged so that a plurality of anode catalyst layers and a plurality of cathode catalyst layers are alternately formed along the longitudinal direction, the bending process is performed. A plurality of membrane electrode assemblies can be manufactured simultaneously.

  In the method for producing a membrane electrode assembly according to the present invention, after the hydrolysis step, the anode catalyst layer and the cathode catalyst layer adjacent to the anode catalyst layer in the longitudinal direction are opposed to each other. It is more preferable to further include a second bending step of bending the laminated body along the hand direction.

  According to the present invention, by performing the second bending step on the strip-shaped membrane electrode assembly produced by the production method, if a separator is disposed between these opposed catalyst layers, It is possible to easily make a fuel cell in which a catalyst layer is formed from one membrane electrode assembly without misalignment without separating (stacking) a plurality of membrane electrode assemblies.

  Furthermore, a plurality of the anode catalyst layers and a plurality of the cathode catalyst layers are alternately formed along the longitudinal direction. As a result, the cathode catalyst layers are always formed on the adjacent anode catalyst layers in the longitudinal direction. Therefore, by performing the second bending step, a plurality of anode catalyst layers having surfaces in the same direction are formed, and a plurality of cathode catalyst layers having surfaces in the same direction opposite to this are formed. become. As a result, when a plurality of membrane electrode assemblies are laminated by the conventional method, it is possible to reliably prevent an assembly error between the anode catalyst layer and the cathode catalyst layer of the membrane electrode assembly.

  Moreover, the manufacturing method of the suitable fuel cell using the manufacturing method of the said membrane electrode assembly is also disclosed as this invention. The method for producing a fuel cell according to the present invention is a method for producing a fuel cell including a method for producing a membrane electrode assembly, wherein the anode catalyst layer and the cathode of the membrane electrode assembly after the second bending step are produced. A diffusion layer is disposed on the surface of the catalyst layer, and a fuel gas flow path is positioned on the anode catalyst layer side between the anode catalyst layer and the cathode catalyst layer facing each other where the diffusion layer is disposed, and the cathode It is more preferable to include a step of arranging a separator in which the fuel gas channel and the oxygen gas channel are formed so that the oxygen gas channel is located on the catalyst layer side.

  According to the method for manufacturing a fuel cell according to the present invention, the separator can be arranged so as to be inserted toward the fold in the short direction of the membrane electrode assembly after the bending step, thereby facilitating the cell formation of the fuel cell. Can be done. That is, as compared with the conventional method of arranging separators between a plurality of membrane electrode assemblies, the number of manufacturing steps can be reduced and the separators can be arranged continuously after the second bending step. In the fuel cell formation, contamination can be suppressed.

  Further, when the diffusion layer and the separator are arranged, the separator having the diffusion layer formed on the surface thereof is arranged on the membrane electrode assembly, so that the diffusion layer and the separator can be arranged on the membrane electrode assembly at the same time. This is preferable because it is possible. However, it is not limited to this method, and if a fuel cell can be manufactured by arranging a diffusion layer and a separator in a membrane electrode assembly, these may be separately arranged.

  The catalyst layer may be arranged by spraying the catalyst by spraying. The catalyst layer is arranged on a backing sheet, and the catalyst layer is heated and pressurized by using a jig or a coating die as an electrolyte layer. May be transferred. If a precursor polymer is also used for the ionomer of the catalyst layer, the membrane electrode assembly can be suitably produced without thermal degradation of the ionomer in the subsequent impregnation step. More preferably, the electrolyte contained in the catalyst layer is a precursor of a fluorine-based electrolyte.

  Moreover, as a diffusion layer, the gas diffusion layer generally used for a fuel cell is used without being specifically limited. For example, a porous conductive sheet mainly composed of a conductive material, a carbon fiber sheet, and the like may be used, and conductive particles such as carbon particles may be further adhered to these using a hydrophobic resin as a binder. . Furthermore, in addition to the gas flow path being formed, the separator is appropriately provided with a structure for discharging water generated during power generation, a structure for circulating a coolant to suppress heat generation of the fuel cell during power generation, etc. May be.

  In the present invention, a composite electrolyte membrane suitably produced by the production method is also disclosed. A composite electrolyte membrane according to the present invention is a composite electrolyte membrane comprising at least an electrolyte layer made of an electrolyte and a reinforcing layer in which a porous polymer material is impregnated with an electrolyte, and the composite electrolyte membrane includes: A radical inhibitor that suppresses the generation of hydroxy radicals by decomposing hydrogen peroxide into water and oxygen, or an additive layer in which a water retention material is added to the electrolyte, and the reinforcing layer formed so as to sandwich the additive layer And the electrolyte layer formed on the surface of each reinforcing layer.

  The composite electrolyte membrane according to the present invention is a composite electrolyte membrane comprising at least an electrolyte layer made of an electrolyte and a reinforcing layer in which a porous polymer material is impregnated with the electrolyte, and the composite electrolyte membrane The membrane includes a first electrolyte layer as the electrolyte layer and a radical inhibitor that is formed so as to sandwich the first electrolyte layer and that suppresses generation of hydroxy radicals by decomposing hydrogen peroxide into water and oxygen, or An additive layer in which a water retaining material is added to the electrolyte, the reinforcing layer formed on the surface of each additional layer, and a second electrolyte layer formed on the surface of each reinforcing layer And an electrolyte layer.

  According to the composite electrolyte membrane of the present invention, as described above, by forming the additive layer to which at least one of the radical suppressing material or the water retention material is added, the fuel cell can generate more power during water movement. These materials can be prevented from moving or being washed away.

  The membrane electrode assembly according to the present invention includes a composite electrolyte membrane in which a reinforcing material sheet made of a porous polymer material is impregnated with an electrolyte sheet made of an electrolyte, or the composite electrolyte membrane according to the invention, and the composite electrolysis membrane A membrane electrode assembly comprising at least a pair of anode catalyst layers and cathode catalyst layers disposed on both sides of the composite electrolyte membrane so as to sandwich the membrane, wherein the membrane electrode assembly is a strip-shaped membrane electrode A plurality of anode catalyst layers and a plurality of cathode catalyst layers are alternately formed along the longitudinal direction on the surface of the membrane electrode assembly.

  According to the membrane electrode assembly according to the present invention, a plurality of anode catalyst layers and a plurality of cathode catalyst layers are alternately formed on the surface of the membrane electrode assembly along the longitudinal direction. The membrane electrode assembly can be bent along the short direction so that the layer and the cathode catalyst layer adjacent to the anode catalyst layer in the longitudinal direction face each other. In the membrane electrode assembly folded in this way, a plurality of anode catalyst layers having surfaces in the same direction are formed, and a plurality of cathode catalyst layers having surfaces in the same direction opposite to this are formed. Become.

  The membrane electrode assembly according to the present invention is bent along the short direction so that the anode catalyst layer and the cathode catalyst layer adjacent to the anode catalyst layer in the longitudinal direction are opposed to each other. Is more preferable.

  The membrane electrode assembly according to the present invention has a structure in which a plurality of anode catalyst layers having surfaces in the same direction are formed, and a plurality of cathode catalyst layers having surfaces in the same direction opposite to this are formed. Therefore, by disposing the diffusion layer and the separator in the bent portion of the membrane electrode assembly, it is possible to easily manufacture the fuel cell without defective assembly of the membrane electrode assembly as in the prior art.

  The fuel cell according to the present invention is a fuel cell including the membrane electrode assembly, and the fuel cell includes the membrane electrode assembly, and the surfaces of the anode catalyst layer and the cathode catalyst layer of the membrane electrode assembly. A fuel gas flow path is formed at least on the anode catalyst layer side between the diffusion layer disposed on the anode layer, and the anode catalyst layer and the cathode catalyst layer facing each other with the diffusion layer disposed thereon, and the cathode catalyst It is preferable to provide a separator having an oxygen gas flow path formed on the layer side. According to the present invention, a fuel cell having a desired number of cells can be easily obtained by cutting a bent portion (a portion of an electrolyte membrane connecting the single cells of the fuel cell) along the short direction of the membrane electrode assembly. Can get to.

  According to the present invention, it is possible to obtain a composite electrolyte membrane having uniform dimensional accuracy while achieving uniform characteristics of the electrolyte in the membrane. In addition, it is possible to obtain a membrane / electrode assembly in which the anode catalyst layer and the cathode catalyst layer are formed so as to sandwich the composite electrolyte membrane without misalignment. Furthermore, it is possible to easily obtain a fuel cell having a desired number of cells with less contamination.

  Below, with reference to drawings, it explains based on some embodiments of the manufacturing method of the composite type electrolyte membrane concerning the present invention.

  FIG. 1 is a schematic diagram showing a method of manufacturing a composite electrolyte membrane (electrolyte membrane) according to the first embodiment, and FIG. 2 is a schematic diagram of a manufacturing apparatus for carrying out the manufacturing method shown in FIG. It is.

  As shown in FIGS. 1 and 2, first, a belt-shaped electrolyte sheet (electrolyte sheet) 11 and a belt-shaped reinforcing sheet 12 made of polytetrafluoroethylene (PTFE), which is a porous polymer material, are prepared. Then, the stacking step A is performed. Specifically, in the laminating step A, the electrolyte sheet 11 and the reinforcing sheet 12 are heated and laminated to produce a laminated body 10A having the electrolyte sheet 11 as the electrolyte layer 11a and the reinforcing sheet 12 as the reinforcing layer 12a.

  The method of laminating the two sheets can be performed by pasting or impregnation. More specifically, as shown in FIG. 2, for example, the electrolyte sheet 11 and the reinforcing sheet 12 are bonded using a pair of rollers 31a and 31b. One surface of the reinforcing sheet 12 is impregnated with a part thereof by being sandwiched and heated and pressurized. The heating temperature at this time is more preferably within the range of 100 to 280 ° C. As a result, the electrolyte sheet 11 and the reinforcing sheet 12 can be integrated. A molten electrolyte may be used instead of the electrolyte sheet 11.

  Next, the bending process B is performed on the stacked body 10 </ b> A manufactured by the stacking process A. Specifically, the laminated body 10B is manufactured by bending the laminated body 10A at the center along the center line L of the laminated body 10A so that the surface (reinforcing layer surface) of the laminated body 10A on the reinforcing layer 12a side overlaps. To do.

  More specifically, as shown in FIG. 2, the rollers 32a and 32b with V-shaped irregularities that rotate along the conveying direction (MD direction) of the laminated body 10A are laminated at the center in the width direction of the laminated body 10A. The body 10A can be bent. Further, the laminated body 10A deformed into a V shape using the rollers 33a and 33b is further bent so that the reinforcing layer 12a of the laminated body 10A overlaps, and the reinforcing layer 12a is heated and pressed by the rollers 33a and 33b. Bond the surfaces of each other. The temperature for heating the laminated body 10A at this time is more preferably within a range of 100 to 280 ° C.

  Next, the laminated body 10B manufactured by the bending process B is inverted by 90 ° with the rollers 34a and 34b, and the impregnation process C is performed on the laminated body 10B. Specifically, the laminate 10B is heated and pressurized until the electrolyte is melted, and the reinforcing layer 12a is impregnated with the electrolyte to produce the laminate 10C.

  More specifically, as shown in FIG. 2, the electrolyte of the electrolyte layer 11a on the surface of the laminated body 10B is made porous by the reinforcing layer 12a by the heat and pressure rollers 35a and 35b rotating along the conveying direction of the laminated body 10B. It is possible to obtain the reinforcing layer 12b impregnated with the quality pores and impregnated with the electrolyte. The temperature at which the laminate 10B is heated at this time is more preferably within the range of 200 to 280 ° C.

  And the hydrolysis process D is performed with respect to the laminated body 10C manufactured by the impregnation process C, an ion exchange function is provided to the electrolyte of the laminated body 10C, and the composite electrolyte membrane 100A can be obtained. As shown in FIG. 2, after the hydrolysis step, the composite electrolyte membrane 100A may be dried and the sheet-like electrolyte membrane 100A may be wound up by a winding device (not shown).

  The composite electrolyte membrane 100A thus obtained is manufactured from only two sheets of the electrolyte sheet 11 and the reinforcing sheet 12, so that the sheets can be easily aligned and the quality of the electrolyte membrane is stabilized. Further, the laminate 10A can be bent and impregnated with the electrolyte of one electrolyte sheet 11. As a result, the homogeneous electrolyte constituting the same electrolyte sheet 11 is disposed on both surfaces of the composite electrolyte membrane 100A, and the thickness of the electrolyte membrane is also stabilized. In this way, it is possible to make the characteristics of the electrolyte in the electrolyte membrane uniform, obtain a highly accurate electrolyte membrane, and stabilize the performance of the fuel cell.

  Further, in the bending step B, the surface on the reinforcing layer 12a side (reinforcing layer surface) overlaps, and the surface on the electrolyte layer 11a side (electrolyte surface) becomes the surface of the laminate 10B. The electrolyte layer 11a is formed on the surface layer, and the position of the reinforcing layer 12a is stabilized. As a result, in the fuel cell including the electrolyte membrane 100A, the surface electrolyte layer 11a suppresses variation in water movement in the surface of the electrolyte membrane 100A during power generation, and further, the electrolyte membrane 100A and the catalyst layer (not shown). ) Can be improved, and the performance can be stabilized.

  Further, if the composite electrolyte membrane 100A is manufactured by the manufacturing method shown in FIG. 2, the stacking process may be performed only by joining two members, and further, it can be performed as a series of processes from the stacking process to the hydrolysis process. The process is simplified, quality control is easy, and mass productivity can be improved.

  FIG. 3 is a view showing a second embodiment of the method for producing a composite electrolyte membrane according to the present invention. The difference from the first embodiment shown in FIG. 1 is that the catalyst layers 13a and 13b are arranged. FIG. 3 shows the steps until the catalyst layer of the membrane electrode assembly (MEA) 50A is formed. Is. The manufacturing method according to the second embodiment includes a laminating step, a bending step, an impregnation step, and a hydrolysis step, and these are denoted by the same reference numerals and detailed description thereof is omitted.

  As shown in FIG. 3, in the lamination step A, the electrolyte sheet 11 and the reinforcing sheet 12 are joined and laminated to produce a laminated body 10A including the electrolyte layer 11a and the reinforcing layer 12a. Next, the anode catalyst layer 13a and the cathode catalyst layer 13b are arranged on the surface of the electrolyte layer 11a after forming the laminate 10A, and the laminate 10D in which the catalyst layers 13a and 13b are formed is manufactured.

  Specifically, in the step J of arranging the catalyst layer, the catalyst layers 13a and 13b may be arranged by spraying the catalyst by spraying, the catalyst layer is arranged on the backing sheet, and the catalyst layer is used as the electrolyte layer. In addition, the image may be transferred by heating and pressing using a jig or a coating die. If the ionomer of the catalyst layer is also a precursor polymer, it is more preferable that the ionomer is not thermally deteriorated in the subsequent impregnation step.

  Next, in the bending step B, the stacked body 10D is bent so that the anode catalyst layer 13a is disposed on one surface of the stacked body 10E and the cathode catalyst layer 13b is disposed on the other surface of the stacked body 10E. Thereafter, in the impregnation step C, the reinforcing layer 12a is impregnated with the electrolyte to produce the laminate 10F, and in the hydrolysis step D, the electrolyte of the laminate 10F is given an ion exchange function to include the composite electrolyte membrane 100B. A membrane electrode assembly 50A can be obtained.

  According to the method for manufacturing the composite electrolyte membrane 100B and the membrane electrode assembly 50A, the anode catalyst layer 13a and the cathode catalyst layer 13b are formed on the same surface where the electrolyte layer 11a of the laminate 10A after the lamination step A is formed. Therefore, the catalyst layers 13a and 13b can be accurately arranged. As a result, in the folding step B, if the accuracy of the folding position of the stacked body 10D can be maintained, the displacement of the anode catalyst layer 13a and the cathode catalyst layer 13b can be suppressed.

  Then, by using the membrane electrode assembly 50A including the electrolyte membrane 100B manufactured in this way for a fuel cell, the assembly failure when assembled as a cell of the fuel cell and the variation in performance of the fuel cell during power generation can be prevented. Can be suppressed. In particular, since the electrolyte layer 11a is stably formed on the surface layer, the adhesion between the electrolyte layer 11a and the catalyst layers 13a and 13b can be improved.

  FIG. 4 is a view showing a third embodiment of the method for producing a composite electrolyte membrane according to the present invention. The manufacturing method according to the third embodiment is different from that of the first embodiment shown in FIG. 1 in that the bending direction in the bending step B is different. In addition, the manufacturing method which concerns on 3rd embodiment includes the lamination process, the impregnation process, and the hydrolysis process, These are attached | subjected the same code | symbol and the detailed description is abbreviate | omitted.

  As shown in FIG. 4, in the lamination step A, the electrolyte sheet 11 and the reinforcing sheet 12 are joined and laminated to produce a laminated body 10A including the electrolyte layer 11a and the reinforcing layer 12a. Next, the bending process B is performed on the stacked body 10 </ b> A manufactured by the stacking process A. Specifically, the laminated body 10A is manufactured by bending the laminated body 10A at the center along the center line L of the laminated body 10A so that the surface (electrolyte layer surface) of the laminated body 10A on the electrolyte layer 11a side overlaps. To do.

  Thereafter, in the impregnation step C, the reinforcing layer 12a is impregnated with the electrolyte to produce the laminate 10H, and in the hydrolysis step D, an ion exchange function is imparted to the electrolyte of the laminate 10H to obtain the composite electrolyte membrane 100C. be able to.

  According to the manufacturing method of the composite electrolyte membrane 100C described above, in the folding step B, the laminate 10A is bent so that the surface of the electrolyte layer 11a overlaps and the reinforcing layer 12a becomes the surface of the electrolyte membrane. The electrolyte layer 11b is formed at the center of the electrolyte membrane 100C in the thickness direction, and the reinforcing layer 12b impregnated with the electrolyte can be disposed in the surface layer near the surface in the thickness direction of the electrolyte membrane. As a result, the creep performance of the electrolyte membrane 100C when using the fuel cell can be improved.

  FIG. 5 is a view showing a fourth embodiment of the method for manufacturing a composite electrolyte membrane according to the present invention, and FIG. 6 is a schematic view of a manufacturing apparatus for carrying out the manufacturing method shown in FIG. The point in which the manufacturing method which concerns on 4th embodiment differs from the thing of 1st embodiment differs in the point which has arrange | positioned the water retention material after a lamination process. In addition, the manufacturing method which concerns on 4th embodiment contains the lamination process, the impregnation process, and the hydrolysis process, and attaches | subjects the same code | symbol and omits the detailed description.

  As shown in FIG. 5, in the lamination step A, the electrolyte sheet 11 and the reinforcing sheet 12 are joined and laminated to produce a laminated body 10A including the electrolyte layer 11a and the reinforcing layer 12a. Next, in the water retaining material arranging step K, the water retaining material 14 is disposed on the surface of the reinforcing layer 12a after the laminated body 10A is formed. Specifically, as shown in FIG. 6, the water retaining material 14 is applied by uniformly disposing on the surface of the reinforcing layer 12a by die coating or spray coating, sputtering, or the like. Specifically, since the water retention material is sandwiched between the reinforcing layers in a bending step B described later, it is preferable that the water retention material is closely attached to the extent that it is not detached at the time of bending. In the case where a fine particle material is used as the water retaining material, as described above, a material having a diameter larger than the pore size of the porous formed in the reinforcing sheet is more preferable in order to sandwich the material during bending.

  Then, in the bending step B, the water retentive material 14 is sandwiched between the reinforcing layers 12a so that the surfaces on the reinforcing layer side are overlapped, and the stacked body 10I is bent to manufacture a stacked body 10J. In the impregnation step C, the electrolyte layer 11a is impregnated with the water retention material 14 and the reinforcing layer 12a to manufacture the laminate 10K, and in the hydrolysis step D, the electrolyte of the laminate 10K is hydrolyzed to have an ion exchange function. To obtain a composite electrolyte membrane 100D.

  In this way, as shown in FIG. 5, along the film thickness direction, the additive layer 14b in which the water retaining material 14 is added as an additive to the electrolyte, and the reinforcing layer formed so as to sandwich the additive layer 14b and impregnated with the electrolyte It is possible to obtain a composite electrolyte membrane 100D including at least 12b and 12b and electrolyte layers 11a and 11a formed on the surfaces of the reinforcing layers 12b and 12b.

  The composite electrolyte membrane 100D manufactured in this way can be fixed at the center in the thickness direction of the electrolyte membrane 100D by being sandwiched during bending with the water retention material 14 as an additive. As a result, it is possible to prevent the water retaining material 14 from moving or being lost due to water movement during power generation of the fuel cell, and to ensure stable proton conductivity.

  FIG. 7 is a view showing a fifth embodiment of the method for producing a composite electrolyte membrane according to the present invention. The manufacturing method according to the fifth embodiment differs from that of the fourth embodiment in that the catalyst layer is different during the lamination process. Note that the manufacturing method according to the fourth embodiment includes an impregnation step, a bending step, and a hydrolysis step, and these are denoted by the same reference numerals and will not be described in detail.

  As shown in FIG. 7, in the lamination step A1, the electrolyte sheet 11 and the reinforcing sheet 12 are joined and laminated, and at the same time, the anode catalyst layer disposed on the backing sheet 81 from the other surface of the electrolyte sheet 11 13a and the cathode catalyst layer 13b are arranged to manufacture the laminate 10L.

  And as above-mentioned, the membrane electrode assembly 50B containing the composite type electrolyte membrane 100E can be obtained through the water retention material arrangement | positioning process K, the bending process B, the impregnation process C, and the hydrolysis process D. At this time, the backing sheet 81 is removed from the laminate 10K after the impregnation step, and after the hydrolysis step, an ion exchange function is imparted to the electrolyte of the laminate 10F, so that the membrane electrode assembly 50B including the composite electrolyte membrane 100E is obtained. Obtainable.

  In this way, as in the second embodiment, the displacement of the anode catalyst layer 13a and the cathode catalyst layer 13b can be suppressed, resulting in poor assembly of the fuel cell and variation in performance of the fuel cell during power generation. Can be suppressed. The composite electrolyte membrane 100E manufactured in this way can fix a water retention material at the center in the thickness direction of the electrolyte membrane 100E. As a result, at the time of power generation of the fuel cell, it is possible to prevent the water retaining material 14 from moving or being lost due to water movement. As a result, proton conductivity can be stably secured.

  FIG. 8 is a view showing a sixth embodiment of the method for producing a composite electrolyte membrane according to the present invention. The point in which the manufacturing method which concerns on 6th embodiment differs from the thing of 4th embodiment differs in the point which has arrange | positioned the water retention material before the lamination process. Note that the manufacturing method according to the fourth embodiment includes a bending step, an impregnation step, and a hydrolysis step, and these are denoted by the same reference numerals, and detailed description thereof is omitted.

  As shown in FIG. 8, the water retention material 14 is first arranged as a pre-process of the stacking process. The arrangement method is the same as in the above embodiment. And in lamination process A2, electrolyte sheet 11 and reinforcement sheet 12 are joined so that water retention material 14 may be arranged between electrolyte sheet 11 and reinforcement sheet 12. Since the joining is performed by impregnating the electrolyte of the electrolyte sheet 11 from one side of the reinforcing sheet 12, the laminated body 10P after the joining is provided with a water retaining material 14 between the electrolyte layer 11a and the reinforcing layer 12a. An additive layer 14b added to the electrolyte as an additive is formed. Thereafter, the composite electrolyte membrane 100F can be obtained through the bending step B, the impregnation step C, and the hydrolysis step D.

  As shown in FIG. 8, the first electrolyte layer 11a as the electrolyte layer and the water retention material formed so as to sandwich the first electrolyte layer 11a in the film thickness direction are added to the electrolyte as an additive. The added additive layers 14b and 14b, the reinforcing layers 12b and 12b formed on the surface of each of the added layers 14b and impregnated with the electrolyte, and formed on the surface of each of the reinforcing layers 12b, A composite electrolyte membrane 100F including the second electrolyte layers 11b and 11b can be obtained.

  The composite electrolyte membrane 100F thus obtained is folded in the folding step B so that the laminate 10A is folded so that the surface of the electrolyte layer 11a overlaps and the reinforcing layer 12a becomes the surface of the electrolyte membrane. The electrolyte layer 11a is formed at the center of the electrolyte membrane 100F in the thickness direction, the reinforcing layer 12b impregnated with the electrolyte is disposed in the surface layer portion near the surface in the thickness direction of the electrolyte membrane, and the additive layer 14b is disposed in the vicinity thereof. Can be made. As a result, not only the creep performance of the electrolyte membrane 100F during use of the fuel cell can be improved, but also the water retention of the electrolyte membrane 100F can be further increased.

  FIG. 9 is a schematic diagram showing a method for manufacturing a membrane electrode assembly according to an embodiment of the present invention, and is a diagram for explaining a second bending with respect to the membrane electrode assembly shown in FIG. 9. As shown in FIG. 9, as in some of the embodiments described above, a strip-shaped electrolyte sheet (electrolyte sheet) 11 and a strip-shaped reinforcement made of polytetrafluoroethylene (PTFE), which is a porous polymer material, are used. A sheet 12 is prepared. Next, in the laminating step A, the electrolyte sheet 11 and the reinforcing sheet 12 are laminated by heating and pressing, and the laminate 10A is manufactured using the electrolyte sheet as the electrolyte layer 11a and the reinforcing sheet 12 as the reinforcing layer 12a.

  Then, the anode catalyst layer 13a and the cathode catalyst layer 13b are arranged on the surface of the electrolyte layer 11a after forming the laminate 10A, and the laminate 10D in which the catalyst layers 13a and 13b are formed is manufactured.

  Specifically, in the step J of disposing the catalyst layer, the anode catalyst layer 13a and the cathode catalyst layer 13b are formed along the short direction S of the laminate 10A on the surface of the electrolyte layer 11a after the formation of the laminate 10A. Are formed in two rows, and a plurality of anode catalyst layers 13a and a plurality of cathode catalyst layers 13b are alternately formed along the longitudinal direction (transport direction) L (in other words, two rows of anode catalysts). The layer 13a and the cathode catalyst layer 13b are formed diagonally), the anode catalyst layer 13a and the cathode catalyst layer 13b are disposed, and they are fixed by pressurizing them and heating them at 170 ° C. or lower. Let

  As in the second embodiment, the catalyst layers 13a and 13b are arranged using a spraying spray catalyst layer, a catalyst layer using a backing sheet, or a jig or a coat die. The arrangement of the catalyst layer by transfer, etc. can be mentioned. If the plurality of catalyst layers 13a, 13b can be arranged in the above-described arrangement on the surface of the desired electrolyte layer 11a, the arrangement method is particularly It is not limited.

  Next, in the bending step B, the anode catalyst layer 13a is disposed on one surface of the stacked body 10E, and the cathode catalyst layer 13b is disposed on the other surface of the stacked body 10E (the anode catalyst layer 13a and the cathode catalyst). The laminated body 10D is bent at the center of the laminated body 10D along the longitudinal direction L (so that the layer 13b sandwiches the laminated body 10E (composite electrolyte membrane)) in the same manner as in some of the above embodiments. Thereafter, in the impregnation step C, the reinforcing layer 12a is impregnated with the electrolyte to produce the laminate 10F, and in the hydrolysis step D, the electrolyte of the laminate 10F is given an ion exchange function to include the composite electrolyte membrane 100B. A membrane electrode assembly 50C can be obtained.

  Since the anode catalyst layer 13a and the cathode catalyst layer 13b are formed along the short direction S in the same plane where the electrolyte layer 11a of the laminate after the lamination process is formed, the composite electrolyte membrane 100B is sandwiched between them. These catalyst layers 13a and 13b can be accurately arranged without positional deviation. As a result, if the accuracy of the folding position of the laminate 10E can be maintained in the bending step B, the positional relationship between the anode catalyst layer 13a and the cathode catalyst layer 13b can be suppressed, and the cell of the fuel cell 1 described later can be suppressed. Assembling failure in the case of assembling as well as variations in performance during power generation of the fuel cell 1 can be suppressed.

  The membrane electrode assembly 50C is a strip-like membrane electrode assembly, and a plurality of anode catalyst layers 13a and a plurality of cathode catalyst layers 13b are formed on the surface of the membrane electrode assembly 50C along the longitudinal direction L. Since these are alternately formed, the fuel cell can be easily manufactured by a second bending step described later.

  Next, the membrane electrode assembly 50C is second bent. Specifically, as shown in FIG. 10, after the hydrolysis step D, in the second bending step, the anode catalyst layer 13a and the cathode catalyst layer 13b adjacent to the anode catalyst layer 13a in the longitudinal direction L , The membrane electrode assembly 50C is bent along the short direction S (along C1-C1, C2-C2,... In the drawing).

  As this bending method, for example, a bending jig having a thickness capable of introducing a separator, which will be described later, is prepared, and the tip of the bending jig is pressed along the short direction S to bend. As long as the adjacent catalyst layers 13a and 13b in the longitudinal direction L can be bent facing each other, the bending method is not particularly limited.

  By performing the second bending step in this way, if a separator or the like to be described later is disposed between the opposed catalyst layers 13a and 13b, one membrane electrode assembly is not laminated. From the continuous membrane electrode assembly 50C, the fuel cell in which the catalyst layers 13a and 13b are formed without misalignment can be easily made into a cell.

  Further, a plurality of anode catalyst layers 13a and a plurality of cathode catalyst layers 13b are alternately formed along the longitudinal direction L, and a cathode catalyst layer 13b is always formed in a layer adjacent to the anode catalyst layer 13a in the longitudinal direction L. Therefore, by performing the second bending step, a plurality of anode catalyst layers 13a having surfaces in the same direction (surfaces in contact with the diffusion layer 15) are formed, and surfaces (diffusion in the opposite direction) are formed. A plurality of cathode catalyst layers 13b having a surface in contact with the layer 15) are formed. As a result, it is possible to reliably prevent an assembly error between the anode catalyst layer and the cathode catalyst layer of the membrane electrode assembly, which may occur when a plurality of membrane electrode assemblies are laminated by the conventional method.

  A method for producing a fuel cell using the membrane electrode assembly produced in this manner will be described in detail below. FIG. 11 is a view showing a method of manufacturing a fuel cell from the membrane electrode assembly 50C shown in FIG.

  In the present embodiment, the fuel cell manufacturing method includes disposing the diffusion layer 15 on the surfaces of the anode catalyst layer 13a and the cathode catalyst layer 13b of the membrane electrode assembly 50C after the second bending step, and disposing the diffusion layer 15 therein. This includes a step of disposing a separator 60 having a fuel gas channel 61 and an oxygen gas channel 62 formed between the anode catalyst layer 13a and the cathode catalyst layer 13b facing each other.

  Specifically, a separator 60 in which a fuel gas channel 61 and an oxygen gas channel 62 are formed is prepared. And the diffusion layer 15 for arrange | positioning on the surface of the anode catalyst layer 13a and the cathode catalyst layer 13b is arrange | positioned on both surfaces of the separator 60. FIG. Furthermore, members 63 having adhesiveness and sealing properties with respect to the membrane electrode assembly 50C are attached to both ends of the separator 60 in the longitudinal direction.

  Then, the separator 60 to which the diffusion layer 15 and the sealant 63 are attached is spread on the surfaces of the anode catalyst layer 13a and the cathode catalyst layer 13b of the membrane electrode assembly 50C toward the bent portion of the membrane electrode assembly 50C. Insert so that 15 is positioned. As a result, a laminated electrode is formed by sandwiching the diffusion layer 15 and the separator 60 on the upper surfaces of the opposing catalyst layers 13a and 13b of the membrane electrode assembly 50C, and is heated and pressurized in the thickness direction. The fuel cell 1 in which the single cells overlap is manufactured.

  Compared with the conventional method which arrange | positions a separator between several membrane electrode assemblies by such a construction method, while being able to reduce a manufacturing man-hour, it arrange | positions a separator continuously after a 2nd bending process. Therefore, contamination of the fuel cell 1 can be suppressed in the cell formation.

  FIG. 12 is a diagram for explaining a method of manufacturing a fuel cell having a desired number of cells from the fuel cell manufactured by the manufacturing method shown in FIG. As shown in FIG. 12, the fuel cell 1 manufactured by the manufacturing method shown in FIG. 11 has a plurality of single-cell fuel cells connected in an insulating state by an electrolyte membrane. Therefore, as shown in FIG. 11, by cutting the electrolyte membrane at the connecting portion, in the module (several to several hundreds) state, in the positional relationship of the cell stacking direction (anode / cathode surface direction) Thus, it is possible to obtain the required number of fuel cells 1A and 1B with no assembly errors.

  As described above, the composite electrolyte membrane, the membrane electrode assembly, the fuel cell, and the manufacturing method thereof according to the present invention have been described in detail. However, the present invention is not limited to the above-described embodiment, and claims Various design changes can be made without departing from the spirit of the invention described in the above.

  For example, in the fourth to sixth embodiments, a water retention material is used as an additive, but during the power generation of a fuel cell, hydrogen peroxide generated as a by-product is decomposed into water and oxygen to generate hydroxy radicals. In order to suppress this, a radical inhibitor made of an oxide of a transition metal such as cerium may be used.

  Moreover, you may cut further the bending edge part used as the folding margin formed at the time of a bending process with the slitter etc. with respect to the composite type electrolyte membrane manufactured in said 1st-6th embodiment.

  Further, although the catalyst layer is further arranged in the second and fifth embodiments, it is of course possible to obtain a fuel cell by arranging the diffusion layer and the separator shown in FIG. 13 in the catalyst layer. It is.

  Further, in the embodiment shown in FIG. 10, when the diffusion layer and the separator are arranged, the separator having the diffusion layer formed on the surface thereof is inserted into the bent portion of the membrane electrode assembly so that the membrane electrode junction is inserted. However, the present invention is not limited to this method. If the diffusion layer and the separator can be arranged in the membrane electrode assembly to produce a fuel cell, these may be arranged separately. In this embodiment, the catalyst layer is disposed after the lamination step. However, if the anode catalyst layer and the cathode catalyst layer can be accurately disposed, the catalyst layer is not disposed on the electrolyte membrane, and the catalyst layer is disposed on the separator. An anode catalyst layer and a cathode catalyst layer may be further disposed on the diffusion layer.

  Further, in the present embodiment shown in FIG. 10, additives such as a water retention agent and a radical inhibitor are not arranged in the composite electrolyte membrane, but the methods shown in the fifth and sixth embodiments in FIGS. 7 and 8 are used. Therefore, additives such as a water retention material and a radical inhibitor may be disposed on the composite electrolyte membrane.

The schematic diagram which showed the manufacturing method of the composite type electrolyte membrane which concerns on 1st embodiment of this invention. The schematic diagram of the manufacturing apparatus for enforcing the manufacturing method shown in FIG. The schematic diagram which showed the manufacturing method of the composite type electrolyte membrane which concerns on 2nd embodiment of this invention. The schematic diagram which showed the manufacturing method of the composite type electrolyte membrane which concerns on 3rd embodiment of this invention. The schematic diagram which showed the manufacturing method of the composite type electrolyte membrane which concerns on 4th embodiment of this invention. The schematic diagram of the manufacturing apparatus for enforcing the manufacturing method shown in FIG. The schematic diagram which showed the manufacturing method of the composite type electrolyte membrane which concerns on 5th embodiment of this invention. The schematic diagram which showed the manufacturing method of the composite type electrolyte membrane which concerns on 6th embodiment of this invention. The schematic diagram which showed the manufacturing method of the membrane electrode assembly which concerns on embodiment of this invention. The figure for demonstrating the 2nd bending with respect to the membrane electrode assembly shown in FIG. The figure which showed the method of manufacturing a fuel cell from the membrane electrode assembly shown in FIG. The figure for demonstrating the method of manufacturing the fuel cell of the desired number of cells from the fuel cell manufactured by the method shown in FIG. It is the figure which showed the manufacturing method of the conventional composite type electrolyte membrane, (a) is a figure for demonstrating the manufacturing method of a composite type electrolyte membrane by the cast film-forming method, (b) is a composite type electrolyte. The figure for demonstrating the method of forming a catalyst layer in a film | membrane by transcription | transfer. The schematic diagram explaining an example of a polymer electrolyte fuel cell (single cell).

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1: Fuel cell, 10A, 10B, ... 10P: Laminated body, 11: Electrolyte sheet, 11a, 11b: Electrolyte layer, 12: Reinforcement sheet, 12a: Porous reinforcement layer, 12b: Reinforcement layer impregnated with electrolyte, 13a, 13b: catalyst layer, 14: water retention material, 14b: additive layer, 50A, 50B, 50C: membrane electrode assembly, 100A, 100B ... 100F: composite electrolyte membrane, A, A1, A2: laminating step, B: Bending process, C: impregnation process, D: hydrolysis process, J: catalyst layer arranging process, K: water retention material arranging process

Claims (3)

A laminating step of heating and laminating an electrolyte sheet made of an electrolyte and a reinforcing sheet made of a porous polymer material to form a strip-shaped laminate including the electrolyte layer and the reinforcing layer;
An anode catalyst layer and a cathode catalyst layer are formed along the short direction of the laminate on the surface of the electrolyte layer after forming the laminate, and a plurality of the anode catalysts are provided along the longitudinal direction. A catalyst layer disposing step of disposing the anode catalyst layer and the cathode catalyst layer so that a layer and a plurality of the cathode catalyst layers are alternately formed;
Along the longitudinal direction, the anode catalyst layer is disposed on one surface of the laminate, and the cathode catalyst layer is disposed on the other surface of the laminate. A first folding step of folding the laminate so that the surfaces overlap;
An impregnation step of heating the laminate after the first folding step until the electrolyte is dissolved, and impregnating the reinforcing layer with the electrolyte;
A hydrolysis step of hydrolyzing the electrolyte impregnated in the laminate;
After the hydrolysis step, the anode catalyst layer and the cathode catalyst layer adjacent to the anode catalyst layer in the longitudinal direction face each other so that the laminate is folded along the short direction. Process,
A diffusion layer is disposed on the surfaces of the anode catalyst layer and the cathode catalyst layer of the laminate after the second folding step, and the anode catalyst layer and the cathode catalyst layer that are opposed to each other with the diffusion layer disposed therebetween. A separator in which the fuel gas channel and the oxygen gas channel are formed such that a fuel gas channel is positioned on the anode catalyst layer side and an oxygen gas channel is positioned on the cathode catalyst layer side Separator placement step of placing the laminate on the laminate,
A method for producing a fuel cell, comprising: In the laminating step, on the surface of the reinforcing layer after forming the laminate, a radical inhibitor that suppresses generation of hydroxy radicals by decomposing hydrogen peroxide into water and oxygen, or water is absorbed and retained. The method for producing a fuel cell according to claim 1 , wherein at least one of the water-retaining materials that can be used is disposed. In the laminating step, between the electrolyte sheet and the reinforcing sheet, hydrogen peroxide is decomposed into water and oxygen to suppress generation of hydroxy radicals, or water can be absorbed and retained. The method for producing a fuel cell according to claim 1 , wherein at least one of the water retention materials is arranged.

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