JP5157050B2 - Membrane electrode assembly and manufacturing method thereof - Google Patents

Description

  The present invention relates to a membrane electrode assembly constituting a fuel cell and a manufacturing method thereof.

2. Description of the Related Art Conventionally, there has been known a membrane electrode assembly that prevents damage to an electrolyte membrane and facilitates a manufacturing process of a fuel cell by impregnating and molding a sealing material at an end portion in an in-plane direction of an electrode layer (Patent Document) 1).
JP-T-2001-510932 (see, for example, Fig. 3A-3C)

  However, when the sealing material is impregnated and molded as described above, a short circuit may occur between the anode and the cathode due to the gas diffusion layer or the catalyst layer biting into the electrolyte membrane due to compressive stress from the mold during molding, or the electrolyte membrane May be damaged.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a membrane electrode assembly capable of preventing occurrence of a short circuit between an anode and a cathode and breakage of an electrolyte membrane during production, and production thereof. It is to provide a method.

In order to solve the above-described problems, a membrane electrode assembly according to the present invention includes an electrolyte membrane having ionic conductivity and a pair of outer dimensions smaller than the outer dimensions of the electrolyte membrane and contacting both surfaces of the electrolyte membrane. And a pair of adhesive layers formed at the ends of the electrolyte membrane and the catalyst layer, and an electrically insulating property bonded to each of the opposite surfaces of the pair of adhesive layers. An electrolyte having a pair of spacer layers, a gas diffusion layer provided on the surfaces of the catalyst layer and the spacer layer, and an impregnation portion formed by impregnating a sealing material in an outer peripheral portion of the gas diffusion layer The membrane is disposed on the inner side in the in-plane direction than the bonding interface position between the gas diffusion layer and the impregnated portion, the adhesive layer is formed on each of the front and back surfaces of the electrolyte membrane, and the spacer layer and the gas diffusion layer Bonding interface and perpendicular to the in-plane direction Disposed in-plane direction outward from the surface, the spacer layer extend in plane inward of the junction interface position between the impregnation unit and the gas diffusion layer, the plane direction outer end portion of the electrolyte membrane, an adhesive layer and the end-plane direction inside of an end portion of the in-plane direction inside the spacer layer, and the ends of the plane outward of the gas diffusion layer, for in-plane direction so as to overlap Oite vertically Has been placed .

In order to solve the above-described problems, a method of manufacturing a membrane electrode assembly according to the present invention contacts a pair of catalyst layers having an outer dimension smaller than the outer dimension of the electrolyte membrane on both surfaces of the electrolyte membrane having ion conductivity. Electrical insulating properties bonded to each of the surface opposite to the surface where the adhesive layers of the pair of adhesive layers face each other, the step of forming a pair of adhesive layers on the ends of the electrolyte membrane and the catalyst layer A step of forming a pair of spacer layers, a step of forming a gas diffusion layer on the surfaces of the catalyst layer and the spacer layer, and a step of forming an impregnation portion by impregnating the outer peripheral portion of the gas diffusion layer with a sealing material An electrolyte membrane is formed on the inner side in the in-plane direction from the bonding interface position between the gas diffusion layer and the impregnated portion, and an adhesive layer is formed on each of the front and back surfaces of the electrolyte membrane, and Joining of spacer layer and gas diffusion layer Formed in the in-plane direction outside the bonding interface perpendicular to the in-plane direction, and the spacer layer is formed by extending inward in the in-plane direction from the bonding interface position between the gas diffusion layer and the impregnation part, An end in the in-plane direction of the electrolyte membrane, an end in the in-plane direction of the adhesive layer, an end in the in-plane direction of the spacer layer , and an end in the in-plane direction of the gas diffusion layer , for the in-plane direction form formed so as to overlap in the vertical direction.

  According to the membrane electrode assembly and the method for producing the same according to the present invention, the spacer layer extends inward in the in-plane direction from the interface position between the gas diffusion layer and the impregnation portion. Since the compressive stress applied to the catalyst layer can be relaxed, the gas diffusion layer and catalyst layer are prevented from biting into the electrolyte membrane due to the compressive stress from the mold, and a short circuit between the anode and the cathode and damage to the electrolyte membrane occur. Can be prevented.

  The membrane electrode assembly according to the present invention can be applied to, for example, a fuel cell stack 1 in which a plurality of fuel cells 2 are stacked as shown in FIG. Hereinafter, the configuration of a fuel cell stack 1 according to an embodiment of the present invention will be described with reference to the drawings.

[Configuration of fuel cell stack]
A fuel cell stack 1 according to an embodiment of the present invention has a configuration in which a plurality of fuel cells 2 are sandwiched by end plates 4 as shown in FIGS. Then, reaction gas (hydrogen gas, air) and cooling water used for power generation are supplied. Further, a separator 3 is provided between the fuel cells 2 as shown in FIG. 2, and the reaction gas supplied from the manifold opening 5 is supplied to the separator 3 from the fuel cell 2 as shown in FIGS. Specifically, a gas flow channel 6 for supplying to the anode and cathode of the fuel cell 2 is formed. In the fuel cell stack 1 having such a configuration, each fuel cell 2 generates power in response to hydrogen gas and air being supplied from the gas flow channel groove 6 to the anode and cathode of each fuel cell 2, respectively. The generated power of each fuel cell 2 is taken out of the system through the end plate 4. The separator 3 can be used without limitation as long as it is known at the time of filing of the present invention, such as those made of carbon such as dense carbon graphite and carbon plate, and those made of metal such as stainless steel. Further, the thickness and size of the separator 3 and the shape of the gas flow channel groove 6 are not particularly limited, and may be appropriately determined in consideration of the output characteristics of the fuel cell 2 and the like.

[Configuration of fuel cell]
The fuel cell 2 further includes a membrane electrode assembly (hereinafter abbreviated as MEA) sandwiched between a pair of catalyst layers functioning as an anode and a cathode and sandwiched between gas diffusion layers. It has a configuration. More specifically, as shown in FIG. 5, the fuel cell 2 has an electrolyte membrane 11 having ion conductivity and an outer dimension smaller than the outer dimension of the electrolyte membrane 11, and is formed on both surfaces of the electrolyte membrane 11. The anode-side and cathode-side catalyst layers 12 that are in contact with each other, the adhesive layer 13 formed at the ends of the electrolyte membrane 11 and the catalyst layer 12, and a pair of spacer layers having electrical insulation bonded to both surfaces of the adhesive layer 13 14, a gas diffusion layer 15 provided on the surfaces of the catalyst layer 12 and the spacer layer 14, and an impregnation portion 16 formed by impregnating the outer peripheral portion of the gas diffusion layer 15 with a sealing material.

  In the fuel cell 2, the spacer layer 14 functioning as a reinforcing layer extends inward in the plane from the interface position between the gas diffusion layer 15 and the impregnation portion 16. In the conventional fuel cell, the reinforcing layer is located outside the interface position between the gas diffusion layer 15 and the impregnation portion 16 in the in-plane direction. The catalyst layer 12 may bite into the electrolyte membrane 11 and a short circuit between the anode and the cathode or damage to the electrolyte membrane 11 may occur.

  On the other hand, in the fuel cell 2 according to the embodiment of the present invention, as described above, the spacer layer 14 extends inward in the in-plane direction from the interface position between the gas diffusion layer 15 and the impregnation portion 16. Since the compressive stress applied to the gas diffusion layer 15 and the catalyst layer 12 can be absorbed and relaxed by the spacer layer 14 during molding, the gas diffusion layer 15 and the catalyst layer 12 bite into the electrolyte membrane 11 by the compressive stress from the mold. This can prevent the occurrence of a short circuit between the anode and the cathode and the breakage of the electrolyte membrane 11.

  In the configuration of the fuel cell 2 shown in FIG. 5, as shown in FIG. 6, a seal portion 17 made of a sealing material impregnated in the impregnation portion 16 may be protruded from the surface of the impregnation portion 16. According to such a configuration, the sealing performance is further improved, and it is not necessary to form a seal portion on the side of the separator 3 facing the fuel cell 2, so that the manufacturing process of the fuel cell stack 1 can be facilitated.

  Further, in the configuration of the fuel cell 2 shown in FIGS. 5 and 6, as shown in FIG. 7, the length in the in-plane direction of one spacer layer 14 of the pair of spacer layers 14 is the surface of the other spacer layer 14. It may be shorter than the inward length. According to such a configuration, since the compressive stress applied to the electrolyte membrane 11 can be dispersed during molding, the durability of the fuel cell 2 can be greatly improved.

  Further, in the configuration of the fuel cell 2 shown in FIGS. 5 to 7, the adhesive layer 13 may be extended inward in the in-plane direction from the spacer layer 14 as shown in FIG. 8. According to such a configuration, since the end portion of the spacer layer 14 does not directly contact the electrolyte membrane 11, the compressive stress applied to the electrolyte membrane 11 at the time of molding is more reliably reduced, and the durability of the fuel cell 2 is greatly increased. Can be improved.

  Further, in the configuration of the fuel cell 2 shown in FIGS. 5 to 8, as shown in FIG. 9, a spacer layer 14 may be provided at the end of the electrolyte membrane 11. Generally, compressive stress for sealing is applied to the impregnated portion 16 and the seal portion 17, but a spacer layer 14 is also provided at the end of the electrolyte membrane 11, in other words, compression creep of the adhesive layer 13, the electrolyte membrane 11, etc. Further, by making a member that easily generates compressive strain into a member that does not easily generate compressive creep or compressive strain, the degree of compressive creep or compressive strain can be suppressed, and the sealing performance can be maintained for a long time.

  Further, in the configuration of the fuel cell 2 shown in FIGS. 5 to 9, as shown in FIG. The seal portion 17 may be integrally formed through the hole. According to such a structure, the impregnation part 16 and the seal | sticker part 17 can be shape | molded by a simpler process.

  Further, in the configuration of the fuel cell 2 shown in FIGS. 5 to 9, as shown in FIG. 11, the seal portion 17 may seal the end portions of the adhesive layer 13, the spacer layer 14, and the impregnation portion 16. Good. According to such a configuration, the thickness of the seal portion 17 is increased, and the ratio of the crushing allowance with respect to the entire thickness of the seal portion 17 can be reduced, so that the compressive strain is suppressed and the sealing performance is maintained for a long time. be able to.

  Further, in the configuration of the fuel cell 2 shown in FIG. 11, as shown in FIG. 12, the seal portion 17 is formed with a manifold opening 18 that communicates with a gas inlet or a gas outlet to the gas diffusion layer 15 to form a spacer layer. At least one of 14 may be passed through the inside of the seal portion 17 in the in-plane direction, and the seal portion 17 may be integrally formed through a through hole formed in the spacer layer 14. According to such a structure, the shape stability and handling property as the fuel cell 2 can be improved.

  Further, in the configuration of the fuel cell 2 shown in FIGS. 5 to 9, as shown in FIG. 13, as shown in FIG. A communicating manifold opening 19 may be formed, and the seal portion 17 may be formed on the surface of the impregnation portion 16 in the in-plane inner direction and the in-plane outer direction with respect to the manifold opening 19. According to such a configuration, the shape in the vicinity of the manifold opening 19 can be stabilized, and the shape stability and handling properties of the fuel cell 2 can be improved.

  Further, in the configuration of the fuel cell 2 shown in FIG. 11, as shown in FIG. 14, a manifold opening 20 that communicates with the gas introduction port or the gas discharge port to the gas diffusion layer 15 is formed in the seal portion 17, and the impregnation portion is formed. At least one of 16 may pass through the inside of the seal portion 17 in the in-plane direction. According to such a structure, the shape stability and handling property as the fuel cell 2 can be improved.

  The fuel cell 2 shown in FIG. 10 can be manufactured by pouring a sealing material into the through hole after the fuel cell 2 is placed on the mold 31 as shown in FIGS. Further, in this case, in order to control the length in the in-plane direction of the impregnated portion 16, a convex portion 32 is formed on the mold 31 as shown in FIG. It is desirable not to impregnate. However, the position of the convex portion 32 is positioned on the outer side in the in-plane direction than the inner end surface in the in-plane direction of the spacer layer 14. Thereby, at the time of molding, it is possible to prevent the gas diffusion layer 15 and the catalyst layer 12 from biting into the electrolyte membrane 11 due to the compressive stress from the mold, thereby preventing a short circuit between the anode and the cathode and damage to the electrolyte membrane 11. .

  The catalyst component used for the catalyst layer 12 on the cathode side is not particularly limited as long as it has a catalytic action for the oxygen reduction reaction, and a known catalyst component can be used. Further, the catalyst component used for the catalyst layer 12 on the anode side is not particularly limited as long as it has a catalytic action for the oxidation reaction of hydrogen, and a known catalyst component can be used.

  More specifically, the catalyst component includes platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), osmium (Os), tungsten (W), lead (Pd ), Iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), vanadium (V), molybdenum (Mo), gallium (Ga), aluminum (Al), etc. These metal alloys can be exemplified.

  Further, as the catalyst component, it is desirable to use a catalyst component containing at least platinum in order to improve catalyst activity, poisoning resistance to carbon monoxide, etc., heat resistance and the like. The composition of the alloy is preferably 30 to 90 atomic% for platinum and 10 to 70 atomic% for the metal to be alloyed, although it depends on the type of metal to be alloyed. Further, when an alloy is used as the catalyst component of the catalyst layer 12 on the cathode side, the composition of the alloy varies depending on the type of metal to be alloyed and the like and can be appropriately selected by those skilled in the art. It is preferable that 90 atomic% and other metals to be alloyed be 10 to 70 atomic%.

  The “alloy” is formed by adding one or more metal elements or non-metal elements to the metal element, and is a generic name for those having metallic properties. In addition, the structure of the alloy includes eutectic alloys, which are so-called mixtures in which the component elements become separate crystals, those in which the component elements are completely melted into a solid solution, and the component elements are intermetallic compounds or metals and nonmetals. Some of them form a compound, and any of them may be used in the present embodiment. At this time, the catalyst component used for the catalyst layer 12 can be appropriately selected from the above. In the following description, unless otherwise specified, the description of the catalyst component for the catalyst layer 12 on the cathode side and the anode side has the same definition for both, and is collectively referred to as “catalyst component”. However, the catalyst components for the catalyst layer 12 on the cathode side and the anode side do not have to be the same, and can be appropriately selected so as to exhibit the desired action as described above.

  The shape and size of the catalyst component are not particularly limited, and the same shape and size as known catalyst components can be used, but the catalyst component is preferably granular. At this time, the smaller the average particle size of the catalyst particles used in the catalyst ink, the higher the effective electrode area where the electrochemical reaction proceeds, and thus the higher the oxygen reduction activity. However, the average particle size is actually small. If the amount is too high, a phenomenon in which the oxygen reduction activity decreases is observed.

  Therefore, the average particle diameter of the catalyst particles contained in the catalyst ink is about 1 to 30 [nm], more preferably about 1.5 to 20 [nm], still more preferably about 2 to 10 [nm], and particularly preferably 2 It is preferable that the particle size is about ˜5 [nm]. Moreover, it is preferable that it is 1 [nm] or more from a viewpoint of the carrying | support ease, and it is preferable that it is 30 [nm] or less from a viewpoint of a catalyst utilization factor. The average particle diameter of the catalyst particles is measured by the crystal particle diameter obtained from the half-value width of the diffraction peak of the catalyst component in X-ray diffraction or the average value of the particle diameter of the catalyst component determined from a transmission electron microscope image. Can do.

  The catalyst particles are included in the catalyst ink as an electrode catalyst supported on a conductive carrier. Note that the conductive carrier is not particularly limited as long as it has a specific surface area for supporting the catalyst particles in a desired dispersed state and has sufficient electronic conductivity as a current collector. Are preferred. More specifically, as a conductive carrier, carbon particles made of carbon black, activated carbon, coke, natural graphite, artificial graphite and the like can be exemplified as a suitable example.

  “The main component is carbon” means that the main component includes carbon atoms, and is a concept including both carbon atoms and substantially carbon atoms. In some cases, in order to improve the characteristics of the fuel cell, the conductive support may contain elements other than carbon atoms. In addition, being substantially composed of carbon atoms means that mixing of impurities of about 2 to 3% by mass or less is allowed.

Further, the BET specific surface area of the conductive carrier may be a specific surface area sufficient to carry the catalyst component in a highly dispersed state, but is preferably about ^{20 to} 1600 [m ² / g], more preferably 80 to 1200. It may be set to about [m ² / g]. If the specific surface area is less than 20 [m ² / g], the dispersibility of the catalyst component and the polymer electrolyte on the conductive support may be lowered, and sufficient power generation performance may not be obtained. If it exceeds [m ² / g], the effective utilization rate of the catalyst component and the polymer electrolyte may be lowered.

  Further, the size of the conductive carrier is not particularly limited, but the average particle size is not limited from the viewpoints of easy loading, catalyst utilization, and control of the thickness of the catalyst layer 12 within an appropriate range. It is desirable that the thickness be about 5 to 200 [nm], preferably about 10 to 100 [nm]. Further, in the electrode catalyst in which the catalyst component is supported on the conductive support, the supported amount of the catalyst component is preferably 10 to 80% by mass, more preferably 30 to 70% by mass with respect to the total amount of the electrode catalyst. Good.

  If the supported amount of the catalyst component exceeds 80% by mass, the degree of dispersion of the catalyst component on the conductive support decreases, and although the supported amount increases, the improvement in power generation performance is small and the economic advantage may be reduced. On the other hand, if the supported amount is less than 10% by mass, the catalytic activity per unit mass is lowered, and a large amount of electrode catalyst is required to obtain the desired power generation performance, which is not preferable. The amount of the catalyst component supported can be examined by inductively coupled plasma emission spectroscopy (ICP).

  The catalyst layer 12 includes a polymer electrolyte in addition to the electrode catalyst. The polymer electrolyte is not particularly limited and a known one can be used. However, it is desirable that the polymer electrolyte be a member having at least high proton conductivity. The polymer electrolytes that can be used are broadly classified into fluorine-based electrolytes containing fluorine atoms in all or part of the polymer skeleton and hydrocarbon-based electrolytes not containing fluorine atoms in the polymer skeleton.

  Examples of the fluorine-based electrolyte include perfluorocarbon sulfonic acid polymers such as Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Co., Ltd.), Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.), Trifluorostyrene sulfonic acid polymer, perfluorocarbon phosphonic acid polymer, trifluorostyrene sulfonic acid polymer, ethylene tetrafluoroethylene-g-styrene sulfonic acid polymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride- A perfluorocarbon sulfonic acid polymer or the like can be exemplified as a suitable example.

  The hydrocarbon electrolytes include polysulfone sulfonic acid, polyaryl ether ketone sulfonic acid, polybenzimidazole alkyl sulfonic acid, polybenzimidazole alkyl phosphonic acid, polystyrene sulfonic acid, polyether ether ketone sulfonic acid, polyphenyl sulfonic acid. Etc. can be illustrated as a suitable example.

  The polymer electrolyte preferably includes a fluorine atom because of its excellent heat resistance and chemical stability. Among them, Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, Asahi Kasei Corporation) Fluorine-based electrolyte such as Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.) can be exemplified as a suitable example.

  In addition, the catalyst component can be supported on the conductive support by a known method. For example, impregnation method, liquid phase reduction support method, evaporation to dryness method, colloid adsorption method, spray pyrolysis method, reverse micelle (micro cell) A known method such as an emulsion method can be used. A commercially available electrode catalyst may be used.

  Further, the catalyst layer 12 is formed on the surface of the electrolyte membrane 11 (or the surface of the electrolyte membrane 11 in a state of partially covering the spacer layer 14) with the catalyst ink composed of the electrode catalyst, the polymer electrolyte, and the solvent as described above. It is formed by coating. At this time, the kind of the solvent is not particularly limited, and a normal solvent used for forming the catalyst layer 12 can be used in the same manner. Specifically, water or lower alcohols such as cyclohexanol, ethanol and 2-propanol can be used as the solvent.

  Further, the amount of the solvent used is not particularly limited, and the same amount as known can be used. However, in the catalyst ink, the electrode catalyst has a desired action, that is, hydrogen oxidation reaction (anode side) and oxygen. Any amount may be used as long as it can sufficiently exhibit the catalytic action for the reduction reaction (cathode side). More specifically, the electrode catalyst is preferably present in the catalyst ink in an amount of 5 to 30% by mass, more preferably 9 to 20% by mass.

  Further, the catalyst ink may contain a thickener. The use of a thickener is effective when the catalyst ink cannot be successfully applied onto a transfer mount. The thickener that can be used in this case is not particularly limited, and known thickeners can be used. For example, glycerin, ethylene glycol (EG), polyvinyl alcohol (PVA), propylene glycol (PG) and the like are preferable. It can be illustrated as an example. The amount of the thickener added when using the thickener is not particularly limited as long as it does not interfere with the above effect, but is 5 to 20% by mass with respect to the total mass of the catalyst ink. Is desirable.

  The preparation method of the catalyst ink is not particularly limited as long as the electrode catalyst, the electrolyte and the solvent, and if necessary, the water-repellent polymer and / or the thickener are appropriately mixed. For example, a catalyst ink can be prepared by adding an electrolyte to a polar solvent, heating and stirring the mixture, dissolving the electrolyte in a polar solvent, and then adding an electrode catalyst thereto. Alternatively, the catalyst ink may be prepared by once dispersing / suspending the electrolyte in a solvent and then mixing the dispersion / suspension with the electrode catalyst. In addition, a commercially available electrolyte solution in which the electrolyte is previously prepared in the other solvent (for example, Nafion solution manufactured by DuPont: Nafion dispersed / suspended in 1-propanol at a concentration of 5 wt%) May be used in the above method as is.

  The catalyst ink 12 thus formed is formed by applying the catalyst ink thus prepared on the electrolyte membrane 11 while covering a part of the spacer 14 layer. At this time, the conditions for forming the catalyst layer 12 on the electrolyte membrane 11 are not particularly limited, and can be used in the same manner as known methods or with appropriate modifications. For example, the catalyst ink is applied on the electrolyte membrane 11 so that the thickness after drying is about 5 to 20 [μm], and is about 25 to 150 [° C.] in a vacuum dryer or under reduced pressure, more preferably 60 to Dry at about 120 [° C.] for 5 to 30 minutes, more preferably for 10 to 20 minutes. In addition, in the said process, when the thickness of the catalyst layer 12 is not enough, the said application | coating and drying process is repeated until it becomes desired thickness.

  The spacer layer 14 may be impermeable to gas, particularly oxygen or hydrogen gas. In general, the spacer layer 14 is an adhesive layer intended to adhere to the end portions of the electrolyte membrane 11 and the catalyst layer 12. 13 and an impermeable layer made of a gas impermeable material. In this case, the material constituting the impermeable layer is not particularly limited as long as it is impermeable to oxygen or hydrogen gas when formed into a film. Specifically, as a material constituting the impermeable layer, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), (polyvinylidene fluoride (PVDF), and the like are illustrated as preferable examples. can do.

  The material that can be used for the adhesive layer 13 is not particularly limited as long as the electrolyte membrane 11 or the catalyst layer 12 and the spacer layer 14 can be closely adhered to each other, but polyolefin, polypropylene, thermoplastic elastomer, etc. Hot-melt adhesives, phenolic and epoxy thermosetting adhesives, acrylic adhesives, olefinic adhesives such as polyester and polyolefin, and the like can be used.

  Moreover, the formation method of the said spacer layer 14 is not restrict | limited in particular, A well-known method can be used. For example, after applying an adhesive on the electrolyte membrane 11 so as to have a thickness of about 5 to 30 [μm] while covering the end portion of the electrolyte membrane 11 or the catalyst layer 12, the gas-impermeable material is added to 10 to 200. A method of applying a thickness of about [μm] and curing it by heating at a temperature of about 25 to 150 [° C.] for 10 seconds to 10 minutes can be used. Further, after the gas-impermeable material is formed into a sheet shape in advance, an adhesive is applied to the impermeable film to form the spacer layer 14, and then this is applied to the electrolyte membrane 11 or while covering a part of the spacer layer 14. You may affix on the electrolyte membrane 11. FIG. At this time, the thickness of the impermeable layer is not particularly limited, but is preferably about 15 to 40 [μm], and the thickness of the adhesive layer 13 is also not particularly limited, but is 10 to 25 [μm]. ] Degree is preferable.

  Further, the electrolyte membrane 11 is not particularly limited, and a membrane made of the same electrolyte as that used for the catalyst layer 12 can be exemplified. In addition, various types of Nafion (registered trademark, manufactured by DuPont) manufactured by DuPont and perfluorosulfonic acid membranes represented by Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.), ion exchange resins manufactured by Dow Chemical Company, and ethylene-4 Fluoropolymer electrolytes such as fluoroethylene copolymer resin membranes, resin membranes based on trifluorostyrene, and hydrocarbon resin membranes with sulfonic acid groups, etc. A molecular electrolyte membrane, a membrane in which a polymer microporous membrane is impregnated with a liquid electrolyte, a membrane in which a porous body is filled with a polymer electrolyte, or the like may be used. The polymer electrolyte used for the electrolyte membrane 11 and the polymer electrolyte used for the catalyst layer 12 may be the same or different, but the adhesion between each catalyst layer 12 and the electrolyte membrane 11 is improved. It is preferable to use the same from the viewpoint.

  The thickness of the electrolyte membrane 11 may be appropriately determined in consideration of the characteristics of the obtained MEA, but is preferably about 5 to 300 [μm], more preferably about 10 to 200 [μm], and particularly preferably. It is desirable to be about 15 to 100 [μm]. The thickness of the electrolyte membrane 11 is preferably 5 [μm] or more from the viewpoint of strength during film formation and durability during MEA operation, and is 300 [μm] or less from the viewpoint of output characteristics during MEA operation. Preferably there is.

  In addition, the electrolyte membrane 11 is not only a fluoropolymer electrolyte or a hydrocarbon-based resin membrane having a sulfonic acid group, but is also made of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) or the like. A thin film impregnated with an electrolyte component such as phosphoric acid or ionic liquid is also included.

  Although the method for forming the catalyst layer 12 or the spacer layer 14 directly on the electrolyte membrane 11 has been described above, the fuel cell 2 may be manufactured by other methods such as a transfer method. In addition, the production method in such a case is not particularly limited, and a known transfer method can be used in the same manner or with appropriate modification. For example, the following method can be used.

  That is, the catalyst ink as prepared above is applied onto a transfer mount and dried to form the catalyst layer 12. In this case, as the transfer mount, a known sheet such as a PTFE (polytetrafluoroethylene) sheet, a PET (polyethylene terephthalate) sheet, or a polyester sheet can be used. The transfer mount is appropriately selected according to the type of catalyst ink to be used (particularly, a conductive carrier such as carbon in the ink).

  In the above process, the thickness of the catalyst layer 12 is not particularly limited as long as the catalyst layer 12 can sufficiently exert a catalytic action on the hydrogen oxidation reaction (anode side) and the oxygen reduction reaction (cathode side). Similar thicknesses can be used. Specifically, the thickness of the catalyst layer 12 is preferably about 1 to 30 [μm], more preferably about 1 to 20 [μm].

  The method for applying the catalyst ink onto the transfer mount is not particularly limited, and a known method such as a screen printing method, a deposition method, or a spray method can be applied in the same manner. Also, the drying conditions of the applied catalyst layer 12 are not particularly limited as long as the polar solvent can be completely removed from the catalyst layer 12.

  Specifically, the coating layer (electrode catalyst layer) of the catalyst ink is dried in a vacuum dryer at about room temperature to 100 [° C.], more preferably about 50 to 80 [° C.] for 30 to 60 minutes. At this time, if the thickness of the catalyst layer 12 is not sufficient, the coating / drying process is repeated until a desired thickness is obtained. Next, after the electrolyte membrane 11 is sandwiched between the catalyst layers 12 thus produced, hot pressing is performed on the laminate.

  At this time, the hot press conditions are not particularly limited as long as the catalyst layer 12 and the electrolyte membrane 11 can be sufficiently closely joined, but are about 100 to 200 [° C.], more preferably 110 to 170 [° C. It is preferable to carry out at a pressing pressure of about 1 to 5 [MPa] with respect to the electrode surface. Thereby, the bondability between the electrolyte membrane 11 and the catalyst layer 12 can be enhanced. After performing the hot press, the MEA composed of the catalyst layer 12 and the electrolyte membrane 11 can be obtained by removing the transfer mount.

  The MEA may have a gas diffusion layer 15 as will be described later. At this time, the gas diffusion layer 15 is peeled off the transfer mount in the above-described method, and the obtained bonded body is further subjected to the gas diffusion layer 15. It is preferable that the catalyst layer 12 is further bonded to the catalyst layer 12 after the catalyst layer 12 and the electrolyte membrane 11 are bonded. Further, after the catalyst layer 12 is formed on the surface of the gas diffusion layer 15 in advance to produce a catalyst layer-gas diffusion layer assembly, the electrode catalyst layer-gas diffusion layer assembly is used as a polymer electrolyte in the same manner as described above. The film may be sandwiched and bonded by hot pressing.

  At this time, the gas diffusion layer 15 used in the MEA is not particularly limited, and a known material can be used in the same manner. For example, carbon woven fabric, paper-like paper body, felt, non-woven fabric The thing etc. which use the sheet-like material which has such electroconductivity and porosity as a base material can be illustrated.

  The thickness of the base material may be appropriately determined in consideration of the characteristics of the gas diffusion layer 15 to be obtained, but may be about 30 to 500 [μm]. If the thickness is less than 30 [μm], sufficient mechanical strength or the like may not be obtained. Conversely, if the thickness exceeds 500 [μm], the distance through which gas, water, etc. permeate becomes longer, which is not desirable. .

  The method for forming the catalyst layer 12 on the surface of the gas diffusion layer 15 is not particularly limited, and known methods such as a screen printing method, a deposition method, and a spray method can be similarly applied. Moreover, the formation conditions on the surface of the gas diffusion layer 15 of the catalyst layer 12 are not particularly limited, and the same conditions as in the conventional case can be applied by the specific formation method as described above.

  In addition, the gas diffusion layer 15 preferably contains a water repellent in the base material for the purpose of further improving water repellency and preventing a flooding phenomenon or the like. The water repellent is not particularly limited, but polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyhexafluoropropylene, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc. Examples thereof include fluorine-based polymer materials, polypropylene, polyethylene and the like.

  In order to further improve the water repellency, the gas diffusion layer 15 may have a carbon particle layer made of an aggregate of carbon particles containing a water repellent on the substrate. The carbon particles are not particularly limited and may be general ones such as carbon black, graphite, expanded graphite and the like. Among them, carbon black such as oil furnace black, channel black, lamp black, thermal black, acetylene black and the like can be exemplified as a suitable example because of excellent electron conductivity and a large specific surface area. The particle size of the carbon particles is preferably about 10 to 100 [nm]. Thereby, the high drainage property by capillary force is obtained, and the contact property with the catalyst layer 12 can be improved.

  Moreover, as a water repellent used for a carbon particle layer, the thing similar to the water repellent mentioned above used for a base material is mentioned. Among these, fluorine-based polymer materials are preferably used because of their excellent water repellency, corrosion resistance during electrode reaction, and the like. In addition, the mixing ratio of the carbon particles to the water repellent in the carbon particle layer may result in insufficient water repellency as expected when there are too many carbon particles. There is a risk that sex may not be obtained. Considering these, the mixing ratio of the carbon particles to the water repellent in the carbon particle layer is preferably about 90:10 to 40:60 in terms of mass ratio.

  Further, the thickness of the carbon particle layer may be appropriately determined in consideration of the water repellency of the gas diffusion layer 15 to be obtained. Further, when the gas diffusion layer 15 contains a water repellent, a general water repellent treatment method may be used. For example, after immersing the base material used for the gas diffusion layer 15 in the dispersion liquid of the water repellent, a method of heating and drying in an oven or the like can be used.

  In the case where a carbon particle layer is formed on the base material in the gas diffusion layer 15, carbon particles, a water repellent, etc. are used as alcohol solvents such as water, perfluorobenzene, dichloropentafluoropropane, methanol and ethanol. A slurry is prepared by dispersing in a solvent, and the slurry is applied on a substrate and dried, or the slurry is once dried and pulverized to form a powder, and this is applied to the gas diffusion layer 15. Use it. Then, it is preferable to heat-process at about 250-400 [degreeC] using a muffle furnace or a baking furnace.

  In addition, the manufacturing method of the joined body including the catalyst layer 12, the electrolyte membrane 11, and preferably the gas diffusion layer 15 is not limited to the method described above. That is, after applying and drying the catalyst ink on the electrolyte membrane 11, hot pressing is performed to join the catalyst layer 12 to the electrolyte membrane 11, and the obtained joined body is sandwiched between the gas diffusion layers 15 to form MEA. The catalyst ink 12 may be applied and dried on the gas diffusion layer 15 to form the catalyst layer 12, and this may be joined to the electrolyte membrane 11 by hot pressing, or may be performed using various known techniques as appropriate. .

  Further, as described above, the electrolyte membrane-electrode assembly produced by the electrolyte membrane-electrode assembly of the present embodiment and the method of the present embodiment are corroded by the carbon carrier used as the catalyst carrier, and the electrolyte membrane-electrode joint. It becomes possible to suppress deterioration of the electrolyte component contained in the body. In addition, the provision of the spacer layer 14 makes it possible to easily determine the area and arrangement of the catalyst layers 12, and it is not necessary to accurately align the catalyst layers 12 in advance. It is highly desirable considering production. Therefore, by using such an electrolyte membrane-electrode assembly, it is possible to provide a highly reliable polymer electrolyte fuel cell having a simple manufacturing process and excellent durability.

  The type of the fuel cell 2 is not particularly limited. In the above description, the polymer electrolyte fuel cell has been described as an example. Examples include acid electrolyte fuel cells represented by acid fuel cells, direct methanol fuel cells, and micro fuel cells. Among them, the polymer electrolyte fuel cell is preferable because it is small in size and can achieve high density and high output. The fuel cell 2 is useful as a stationary power source in addition to a power source for a moving body such as a vehicle in which a mounting space is limited. Particularly, the fuel cell 2 is used for an automobile in which system start / stop and output fluctuation frequently occur. It can be particularly preferably used.

  In addition to a stationary power source, the polymer electrolyte fuel cell is useful as a power source for a mobile body such as an automobile in which a mounting space is limited. Above all, the power supply for mobile vehicles such as automobiles, which is likely to cause corrosion of the carbon support due to the high output voltage required after a relatively long shutdown, and to deteriorate the polymer electrolyte due to the high output voltage being taken out during operation. It is particularly preferred to be used as

  Examples of the material impregnated in the end portion of the gas diffusion layer 15 include rubber, resin, carbon, and inorganic materials. The rubber includes ethylene-propylene rubber, fluorine rubber, silicone rubber, fluorosilicone rubber, butyl rubber, hydrogenated styrene butadiene rubber, hydrogenated styrene isoprene rubber, acrylic rubber, fluoroacrylic rubber and other saturated rubber, or polyester elastomer. Saturated elastomers such as polyolefin elastomers and polyamide elastomers are used. Alternatively, saturated liquid rubbers such as liquid silicon rubber, liquid fluorosilicone rubber, liquid fluororubber, liquid butyl rubber, and liquid ethylene propylene rubber are used.

  In addition, as a resin, a thermosetting resin such as silicon resin, epoxy resin, phenol resin, thermosetting polyimide resin, diallyl phthalate resin, or polyolefin resin, polysulfone resin, polyester resin, polyamide resin, Thermoplastic resins such as polyimide resin, polyamideimide resin, polycarbonate resin, fluorine resin, polyetherimide, polyetheretherketone, polystyrene, polyphenylene sulfide, and polyphenylene ether are used. Further, as the carbon, carbon black, carbon powder, graphite powder, carbon fiber, graphite fiber, or the like is used. As the inorganic material, glass powder, glass fiber, or metal oxide material is used.

  As mentioned above, although the embodiment to which the invention made by the present inventor is applied has been described, the present invention is not limited by the description and the drawings that form part of the disclosure of the present invention according to this embodiment. As described above, it is a matter of course that all other embodiments, examples, operation techniques, and the like made by those skilled in the art based on the above embodiments are included in the scope of the present invention.

It is a perspective view which shows the structure of the fuel cell stack used as embodiment of this invention. 1 is an exploded perspective view of a fuel cell stack according to an embodiment of the present invention. It is a top view which shows the structure of the separator used as embodiment of this invention. It is sectional drawing which shows the structure of the separator used as embodiment of this invention. It is sectional drawing which shows the structure of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is sectional drawing which shows the structure of the modification of the fuel cell used as embodiment of this invention. It is a figure for demonstrating the manufacturing method of the fuel cell shown in FIG. It is a figure for demonstrating the manufacturing method of the fuel cell shown in FIG. It is a figure for demonstrating the application example of the manufacturing method of the fuel cell shown in FIG.

Explanation of symbols

1: Fuel cell stack 2: Fuel cell 3: Separator 4: End plate 5: Manifold 6: Gas passage groove 11: Electrolyte membrane 12: Catalyst layer 13: Adhesive layer 14: Spacer layer 15: Gas diffusion layer 16: Impregnation part 17: Seal part

Claims (11)

An electrolyte membrane having ionic conductivity;
A pair of catalyst layers having an outer dimension smaller than the outer dimension of the electrolyte membrane and contacting both surfaces of the electrolyte membrane;
A pair of adhesive layers formed at the ends of the electrolyte membrane and the catalyst layer;
A pair of spacer layers having electrical insulating properties, which are bonded to each of the opposite surface and the opposite surface of the pair of adhesive layers;
A gas diffusion layer provided on the surfaces of the catalyst layer and the spacer layer;
An impregnated part formed by impregnating a sealing material on the outer peripheral part of the gas diffusion layer,
The electrolyte membrane is disposed on the inner side in the in-plane direction than the bonding interface position between the gas diffusion layer and the impregnation portion,
The adhesive layer is formed on each of the front and back surfaces of the electrolyte membrane, and is a bonding interface between the spacer layer and the gas diffusion layer and is outside in the in-plane direction from the bonding interface perpendicular to the in-plane direction. Placed in
The spacer layer extends inward in the in-plane direction from the bonding interface position between the gas diffusion layer and the impregnation part,
An end in the in-plane direction of the electrolyte membrane, an end in the in-plane direction of the adhesive layer, an end in the in-plane direction of the spacer layer, and an end in the in-plane direction of the gas diffusion layer The part is disposed so as to overlap in the direction perpendicular to the in-plane direction. The membrane electrode assembly according to claim 1,
A membrane / electrode assembly comprising a seal portion made of the sealing material protruding and formed on the surface of the impregnation portion. The membrane electrode assembly according to claim 1 or 2, wherein
Among the pair of spacer layers, the length in the in-plane direction of one spacer layer is shorter than the length in the in-plane direction of the other spacer layer. The membrane electrode assembly according to any one of claims 1 to 3, wherein
A second spacer layer having electrical insulation at an end of the electrolyte membrane;
The membrane electrode assembly, wherein the second spacer layer is disposed between the pair of spacer layers . The membrane electrode assembly according to claim 2 , wherein
A membrane electrode assembly comprising a through-hole penetrating the adhesive layer, the spacer layer, and the impregnated portion in a plane vertical direction, wherein the seal portion is integrally formed through the through-hole . The membrane electrode assembly according to claim 2 , wherein
Prior Symbol seal portion, the adhesive layer, the spacer layer, and the membrane electrode assembly, characterized in that sealing the end of the impregnation section. The membrane electrode assembly according to claim 6 , wherein
The seal portion has a manifold opening communicating with the gas inlet or gas outlet Previous SL gas diffusion layer, at least one of the spacer layer through the interior of the sealing portion in the plane direction, the seal The membrane electrode assembly is characterized in that the portion is integrally formed through a through-hole formed in the spacer layer . The membrane electrode assembly according to claim 2 , wherein
The adhesive layer, the spacer layer, and the impregnated portion have a manifold opening communicating with a gas inlet or a gas outlet to the gas diffusion layer, and the seal portion is in an in-plane inner direction with respect to the manifold opening. A membrane electrode assembly, wherein the membrane electrode assembly is formed on the surface of the impregnation portion in the in-plane outer direction . The membrane electrode assembly according to claim 6 , wherein
The seal portion has a manifold opening communicating with a gas introduction port or a gas discharge port to the gas diffusion layer, and at least one of the impregnation portions penetrates the inside of the seal portion in an in-plane direction. A membrane electrode assembly. Contacting a pair of catalyst layers having outer dimensions smaller than the outer dimensions of the electrolyte membrane on both surfaces of the electrolyte membrane having ion conductivity;
Forming a pair of adhesive layers at the ends of the electrolyte membrane and the catalyst layer;
Forming a pair of spacer layers having electrical insulation bonded to each of the opposite surfaces of the pair of adhesive layers facing each other;
Forming a gas diffusion layer on the surfaces of the catalyst layer and the spacer layer;
Forming an impregnated part by impregnating a sealing material on an outer peripheral part of the gas diffusion layer,
The electrolyte membrane is formed on the inner side in the in-plane direction than the bonding interface position between the gas diffusion layer and the impregnation portion,
The adhesive layer is formed on each of the front and back surfaces of the electrolyte membrane, and is a bonding interface between the spacer layer and the gas diffusion layer and is outside in the in-plane direction with respect to the bonding interface perpendicular to the in-plane direction. Formed into
The spacer layer is formed by extending inward in the in-plane direction from the bonding interface position between the gas diffusion layer and the impregnation part,
An end in the in-plane direction of the electrolyte membrane, an end in the in-plane direction of the adhesive layer, an end in the in-plane direction of the spacer layer, and an end in the in-plane direction of the gas diffusion layer a Department, formed to a manufacturing method of the membrane electrode assembly, wherein Rukoto to overlap in a direction perpendicular to the plane direction. It is a manufacturing method of the membrane electrode assembly according to claim 10,
A method for producing a membrane electrode assembly, comprising a step of projecting a seal portion made of the sealing material on the surface of the impregnation portion .

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