WO2004107487A1 - 燃料電池用発電体、該燃料電池用発電体の製造方法、該燃料電池用発電体の製造に用いる成形型及び該燃料電池用発電体を用いた燃料電池 - Google Patents
燃料電池用発電体、該燃料電池用発電体の製造方法、該燃料電池用発電体の製造に用いる成形型及び該燃料電池用発電体を用いた燃料電池 Download PDFInfo
- Publication number
- WO2004107487A1 WO2004107487A1 PCT/JP2004/007076 JP2004007076W WO2004107487A1 WO 2004107487 A1 WO2004107487 A1 WO 2004107487A1 JP 2004007076 W JP2004007076 W JP 2004007076W WO 2004107487 A1 WO2004107487 A1 WO 2004107487A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fuel cell
- power generation
- power generator
- generation body
- proton conductor
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- Power generator for fuel cell method for manufacturing power generator for fuel cell, molding die used for manufacturing power generator for fuel cell, and fuel cell using power generator for fuel cell
- the present invention relates to a fuel cell power generator and a fuel cell, in which a pair of electrodes are joined in an opposite manner on both sides of an electrolyte layer.
- a fuel cell basically generates hydrogen by reacting hydrogen and oxygen in a power generation body having electrodes disposed on both sides of an electrolyte layer, and converts chemical energy generated at that time into electric energy. It is converted, and is attracting attention as a clean and highly efficient system.
- the characteristics of the fuel cell such as the operating temperature, differ greatly depending on the material of the ion conductor (usually a proton conductor) constituting the electrolyte layer, and the fuel cell is classified according to the type of the ion conductor.
- so-called polymer electrolyte fuel cells operate at around room temperature and are expected to be useful for automobiles and mobile phones.
- This solid polymer type fuel cell uses an ion exchange polymer membrane which is a proton conductor for the electrolyte layer. Then, usually, the ion exchange polymer membrane is formed by thermocompression bonding a pair of electrodes comprising a catalyst layer carrying a catalyst such as platinum on one side and a gas diffusion conductive layer for diffusing the supplied gas.
- a plurality of unit cells formed by sandwiching the power generation body between a pair of separators having gas flow grooves are electrically connected. Construct a fuel cell.
- these ion exchange polymer membranes those using perfluorosulfonic acid ion exchange membranes represented by Nafion (Nafion (registered trademark)) are the most developed and are approaching the stage of practical use. .
- Patent Document 1 Japanese Patent Application Laid-Open No. 2002-313358 Disclosure of the Invention Problem to be Solved by the Invention
- Powder power of phosphate glass obtained by the melting method It reacts with water at normal temperature and changes to a highly viscous gel comprising a dispersed phase consisting of phosphate molecular chains and a dispersion medium consisting of water.
- Such gel is found to be a proton conducting gel having high ionic conductivity near room temperature (Japanese Patent Application No. 2002-007686).
- Japanese Patent Application No. 2002-007686 Japanese Patent Application No.
- this proton conducting gel comprises a dispersed phase consisting of a phosphate molecular chain in which a phosphorus group is bonded to a phosphorus atom, and said phosphate molecular chain
- the phosphate molecular chains that make up the dispersion medium have a linear shape by analysis such as liquid chromatograph. It has been shown to be either a structure or an annular structure. That is, in such a proton conducting gel, the phosphate glass powder reacts with water, and the phosphate molecular chains constituting the phosphate glass are divided at a circle group, and thus they are divided into multiple phosphorus atoms.
- the phosphate molecular chain to which an amount of ⁇ group is bound is a dispersed phase, and a large amount of water present around each ⁇ group of the phosphate molecule chain is a dispersion medium.
- the acid group of the phosphate molecular chain dissociates protons immediately because phosphoric acid is strongly acidic, in this proton conducting gel, water molecules and other molecules coordinated around the dissociated proton force It is thought to be sequentially transmitted via a proton conduction pathway consisting of a cage group.
- this proton conducting gel exhibits proton conductivity higher than that of the above-mentioned Nafion near the general operating temperature (80 ° C.) of the polymer electrolyte fuel cell, and the proton conductivity is the temperature and humidity. It is also clear that it is stable against changes, and furthermore, in addition to its excellent proton conductivity, it can be manufactured at a much lower cost compared to the naphth ion, so this proton is If a conductive gel can be suitably used as an electrolyte layer, an excellent fuel cell can be provided at low cost.
- the proton conductive gel is usually highly viscous, it is easy to spread into an equal thickness film having a thickness of 1 mm or less, which is required for the electrolyte of the fuel cell power generator, but it is flexible. Because the shape is unstable, it is difficult to handle. Therefore, if a powerful proton conducting gel can be made tangible, further usefulness as an electrolyte layer of a fuel cell power generator is expected.
- the present invention provides a dispersed phase comprising the above-mentioned phosphate molecular chain and water which can meet such expectations.
- a method of manufacturing the fuel cell power generator a method of manufacturing the fuel cell collector
- An object of the present invention is to provide a mold used and a fuel cell using the fuel cell power generator.
- phosphate glass obtained by a melting method reacts with water to generate phosphorus atoms.
- a dispersion phase comprising a phosphate molecule chain having a linear structure or / and a cyclic structure formed by bonding of an OH group, and a dispersion medium comprising water present around each OH group of the phosphate molecule chain
- a high-viscosity proton conductor having as its main component a proton-conductive gel having an electrolyte layer formed by curing phosphate hydrate crystals to form an equal-thick film shape, and an electrolyte layer of the electrolyte layer
- a fuel cell power generator comprising electrodes provided on both sides in close contact with the curing thereof (Claim 1).
- the present inventors reacted the phosphate glass powder described above with water, and the proton conductive gel obtained was allowed to hydrate in the phosphate buffer by leaving it under conditions that prevented drying. It has been discovered that crystalline crystals precipitate, lose their fluidity, and gradually harden, and solidify as a complex consisting of the phosphate hydrate crystals and an amorphous gel phase. It was also revealed that this cured composite had the same excellent proton conductivity as in the gel state before curing. Therefore, as the electrolyte of the fuel cell power generator, one obtained by curing such a proton conductor was used.
- the electrolyte layer having the above-mentioned excellent proton conductivity is in close contact with the catalyst layer without a gap, a high electromotive force with high reaction efficiency can be obtained.
- the material of the electrolyte layer is inexpensive, it can be manufactured inexpensively.
- the electrolyte layer hardens and is difficult to deform. Further, since the electrolyte layer and the electrodes on both sides are in close contact and integrated, handling is very easy. This fuel cell power generator will be described later. As described above, similar to the conventional solid polymer fuel cell, by interposing a plurality of separators in which the gas flow channel is formed and connecting a plurality of them, an excellent fuel cell can be manufactured at low cost.
- a phosphate molecular chain constituting a proton conductor of the electrolyte layer is used as a dispersed phase.
- the proton conducting gel is obtained by reacting phosphate glass powder with water.
- the phosphate constituting the phosphate glass powder when at least calcium phosphate, zinc phosphate, and magnesium phosphate are contained, a proton conductive gel can be suitably obtained.
- calcium phosphate is the most easily gelled. That is, preferably, the phosphate molecular chain constituting the dispersed phase of the proton conducting gel contains Ca 2+ .
- the phosphoric acid molecular chain in the proton conducting gel has a phosphoric acid in terms of PO of 40 60
- the proton conductor constituting the fuel cell power generator of the present invention is not limited to the proton conductive gel described above, and only the one composed of the complex of the gel and the phosphate hydrate crystal as described above. In addition, as long as it hardens from a high viscosity state and has appropriate proton conductivity, it is possible to use a mixture of the proton conducting gel or the complex with another type of proton conducting substance, a water retention agent, etc. Mm.
- the fuel cell power generator in which the electrolyte layer made of the cured proton conductor and the electrode are joined and integrated, is difficult to join by the thermocompression bonding method used for the ion exchange polymer membrane. Because of this, a new method for closely bonding the electrolyte layer and the electrode is required.
- a phosphate glass obtained by a melting method is reacted with water between a pair of electrodes consisting of a gas diffusion conductive layer and a catalyst layer and having the catalyst layer as an inner side, whereby phosphorus atoms are produced.
- a dispersed phase consisting of a phosphate molecule chain of a linear structure or / and a cyclic structure formed by bonding of an OH group to another, and a dispersion composed of water present around each HH group of the phosphate molecule chain
- the membrane is formed into an equal thickness film shape intervened by a highly viscous proton conductor mainly composed of a proton conductive gel having a solvent, and then proton hydrate is precipitated by depositing phosphate hydrate crystals in the proton conductor.
- a method of manufacturing a fuel cell power generator is proposed, characterized in that the conductor is cured to form an electrolyte layer (Claim 3).
- the highly viscous proton conductor is formed into a film of equal thickness between the electrodes, and is brought into contact with the catalyst layer side of the electrodes. Then, the proton conductor slightly penetrates into the micropores on the surface of the electrode to be in close contact with the electrode. Then, by curing the proton conductor in a strong state, the electrolyte layer is integrated with the electrode, and a mechanically stable power generator for a fuel cell is manufactured.
- the electrolyte layer needs to be completely solid, as long as it has strength enough to be integrated with the electrode and mechanically stable. Therefore, “hardening” as used herein includes not only changing the proton conductor completely to the solid state, but also changing the proton conductor to the near solid state.
- a pair of electrodes constituting the fuel cell power generator of the present invention has a catalyst layer such as platinum and the like on one surface as used in a conventional solid polymer type fuel cell, and a catalyst layer and gas diffusion.
- a porous conductive pair in which a conductive layer is formed can be used, and carbon paper can be suitably used as an electrode material.
- a lower mold having a molding recess and a support surface on the upper surface, and the lower mold on the lower surface
- a fuel cell power generating body is formed, which has at least a part of a molding recess between the upper and lower molds in an overlapping state of the support surface and the press surface, comprising an upper mold provided with a press surface pressing against the support surface.
- the catalyst layer is placed upward in the molding recess of the lower mold using the molding die in which the closing cavity for forming the cavity and the electrolyte reservoir groove communicating with the closing cavity are formed, and then After supplying a highly viscous proton conductor on one side electrode and placing the other side electrode with the catalyst layer facing downward above it, close the cavity by pressing the upper mold onto the lower mold from above. Inside, with a proton conductor interposed between a pair of electrodes, While forming into a shape, the excess proton conductor is discharged into the electrolyte storage groove, and then the proton conductor is hardened by depositing phosphate hydrate crystals in the proton conductor to form an electrolyte layer.
- a manufacturing method is proposed (claim 4).
- a pair of electrodes sandwiching a proton conductor in a highly viscous state is enclosed in the closure cavity of the mold so that the two electrodes are disposed at a predetermined distance.
- the proton conductor between the electrodes is formed into a membrane-shaped electrolyte layer having a thickness of 1 mm or less in close contact with both electrodes.
- an electrolyte reservoir groove communicating with the closed cavity is formed around the closed cavity of the mold (claim 7)
- the excess proton conductor is separated from the periphery between the electrodes.
- the flexible proton conductor is reliably formed into a thin plate shape without being pushed into the electrolyte storage groove and an excessive pressure is not applied in the closed cavity.
- the proton conductor disposed on the electrode becomes a catalyst. Since it penetrates deep into the layer and interferes with the contact of hydrogen or oxygen with the catalyst, it penetrates slightly to the surface of the chemical reaction electrode, and has a viscosity high enough to be flexibly deformed by clamping pressure from both electrodes. Is desirable.
- the viscosity of this proton conductor differs depending on the type of phosphate molecular chain that constitutes the material proton conduction gel and the additives as described above, the water content and the precipitation in the proton conductor are also different.
- the viscosity of the proton conductor can be appropriately adjusted by adjusting the water content of the proton conductor and the amount of phosphate hydrate crystals contained therein.
- the water content it is possible to separate a proton conducting gel having a required viscosity by centrifuging a proton conducting gel obtained by reacting phosphate glass powder with water.
- the above-mentioned forming die is provided with a forming recess which constitutes at least the lower side of the closure cavity on the upper surface of the lower die, and a slide in the upper and lower direction communicating with the forming recess at the bottom of the forming recess.
- a moving hole is provided, and the sliding hole is internally fitted so as to be capable of moving up and down, and a molding position where the upper surface is aligned with the bottom surface of the molding recess, and the top surface protrudes from the bottom surface of the molding recess, And a pusher for converting the position of the power generation body to an extraction position for pushing the power generation body upward (claim 8). If the power generation body fitted in the molding recess is pushed out from the lower side by the pusher, it becomes possible to easily take out the molding recess force which can not deform the power generation body by applying an inadvertent force.
- the above-mentioned power generation body is used in the fuel cell provided with a plurality of unit cells in which a power generation body formed by joining electrodes in opposite directions on both surfaces of an electrolyte layer is sandwiched between a pair of separators.
- a fuel cell is proposed in which a gas flow passage groove is provided in each of the power generation body contact portions of the pair of separators in surface contact with the power generation body. (Claim 9) With such a configuration, as described above, a mechanically stable fuel cell with high power generation efficiency can be obtained.
- the proton conductor can be manufactured inexpensively as compared with the ion exchange polymer membrane such as the above-mentioned naphth ion, and the manufacturing cost of the fuel cell can be suppressed.
- the power generation body described above can have a force S to be held using the separator of the conventional configuration in which the gas flow channel is formed.
- the electrolyte layer is gradually deformed, and the electrolyte layer is easily damaged in a short period of time.
- the holding force is too weak, the contact between the power generation body and the separator becomes loose, and the power generation efficiency decreases due to the contact resistance between the separator and the power generation body. Is required.
- the surface of the pair of separators facing the power generation body is divided into a power generation body contact portion provided with a gas flow passage groove and a spacer support portion around the power generation body contact portion.
- a configuration is proposed in which an annular spacer is provided between the spacer support portions of both separators to define a predetermined distance between the power generation body contact portions of both separators (claim 10).
- the hard annular spacer is in contact with both spacer supporting portions of the separator. If the generator contacts are supported so that they do not come closer to each other, the generator can be prevented from being deformed or broken by applying an excessive pressure force S.
- Such an annular spacer can be manufactured by a hard insulator such as Teflon (registered trademark).
- the power generation body is in the form of a thin plate in which the outer edges of both the electrodes and the electrolyte layer are identical, and a plurality of power generation bodies project inwardly from the inner edge of the annular spacer and abut on the outer edges of the power generation body.
- Support projection And the sealing gap for filling the sealing agent is formed between the inner edge of the annular spacer in the unit cell and the outer edge of the power generation body (claim 11). The space between the spacers is securely sealed to prevent gas mixing through the outer edge of the generator.
- the sealing agent is required to have insulation property, heat resistance, high viscosity at the time of filling, etc., and silicone grease is suitably used.
- a highly viscous proton conductor mainly composed of a proton conducting gel having a dispersion phase consisting of phosphate molecular chains and a dispersion medium consisting of water is a phosphate water
- a fuel cell power generation body in which electrodes are integrally joined to both sides of the electrolyte layer by depositing an inorganic crystal and curing it into an equal thickness film shape (claim 1)
- the proton conductor constituting the electrolyte layer is excellent in proton conductivity and low in manufacturing cost.
- the cured electrolyte layer and the electrode are integrated and easy to handle, by using the fuel cell power generator of the present invention, a fuel cell with excellent power generation efficiency can be manufactured inexpensively.
- Such a fuel cell power generating body is formed into a uniform film shape by interposing a highly viscous proton conductor mainly composed of the proton conducting gel between a pair of electrodes with the catalyst layer inside. After the formation, the phosphate hydrate crystal is precipitated in the proton conductor, and the proton conductor is hardened (Claim 3). It becomes possible to manufacture as an integral solid.
- a closed cavity for forming a fuel cell power generating body and an electrolyte reservoir in communication with the closed cavity are formed of an upper die and a lower die, and in a state where both dies are superimposed.
- the catalyst layer is placed on the upper side of the lower side of the lower mold using the mold in which the groove is formed, and then the highly viscous proton conductor is supplied on the first side, Furthermore, after arranging the other side electrode with the catalyst layer facing downward above it, press-bonding the upper mold onto the lower mold from above, within the closed cavity generated between the upper and lower mold, proton conduction between the pair of electrodes
- the high viscosity proton conductor is disposed. Push the pair of electrodes into the closing cavity and close it A predetermined width in Yabiti By specifying, the proton conductor between the electrodes can be formed into an electrolyte layer having an equal
- the formed fuel cell power generation body is heat-treated under the conditions of humidity 60-100% RH and temperature 60 100 ° C. (5), the precipitation of phosphate hydrate crystals in the proton conductor is promoted, and the electrolyte layer is rapidly cured to produce a fuel cell power generator.
- the manufacturing time can be shortened.
- the proton-conducting genole When it is contained in the range of 7-55 mol% (claim 2, claim 6), the proton-conducting genole has sufficient proton conductivity and is easy to gel and has high mass productivity.
- the proton conductor used for the fuel cell power generator of the present invention can be manufactured easily and in large quantities.
- a closure cavity for molding a fuel cell power generation body and an electrolyte storage groove communicating with the closure cavity are formed between the upper and lower molds.
- a fuel cell is provided, in which gas flow grooves are respectively provided in the power generation body contact portions of the pair of separators sandwiching the power generation body using the above power generation body, in contact with the power generation body.
- the electrolyte layer is made of a low-cost material with excellent proton conductivity, it can be manufactured at high power generation efficiency and at extremely low cost. Therefore, it can be a mainstream fuel cell used for automobiles, mobile phones, etc., instead of the conventional solid polymer type fuel cell using ion exchange membrane such as naphth ion.
- the surface of the pair of separators facing the power generation body is divided into a power generation body contact portion provided with a gas flow passage groove and a spacer support portion around the power generation body contact portion.
- the power generation body is in the form of a thin plate in which the outer edges of both the electrodes and the electrolyte layer are coincident, and a plurality of power generation members protruding inwardly from the inner edge of the annular spacer abut the outer edges of the power generation body.
- the outer edge of the power generating body is formed by providing a support projection of the battery and forming a sealing gap for filling the sealing agent between the inner edge of the annular spacer in the unit cell and the outer edge of the power generating body.
- the sealing agent ensures that the fuel cell is sealed and prevents the reduction in the power generation efficiency of the fuel cell due to the gas mixture in both electrodes.
- the fuel cell power generator 1 of the present embodiment (hereinafter referred to as power generator 1) comprises an electrolyte layer 6 of equal thickness and a pair of electrodes joined in opposite fashion on both sides of the electrolyte layer 6. It consists of the fuel electrode 2 and the air electrode 3.
- the proton conductor 7 constituting the electrolyte layer 6 is a proton conducting gel (hereinafter simply referred to as a proton conducting gel) having a dispersion phase consisting of phosphoric acid force chains and a dispersion medium consisting of water, and the proton conduction gel It is constituted by a solid complex composed of calcium phosphate hydrate crystals precipitated therein.
- This electrolyte layer 6 has a film shape of 1 mm or less in thickness whose outer edge is matched with the electrodes 2 and 3 and has appropriate mechanical strength. Further, when the proton conducting gel is further specified in detail, the phosphate glass obtained by the melting method reacts with water to form a linear structure or Z and a ring structure in which an ⁇ H group is bonded to a phosphorus atom. And a dispersion medium consisting of water present around each HH group of the phosphate molecular chain.
- a pair of fuel electrode 2 and air electrode 3 are formed by cutting out porous carbon paper having a thickness of 1 mm or less in a predetermined shape. Then, carbon carrying platinum is adhered to one side surface to form a catalyst layer 4, and a portion other than the catalyst layer 4 is used as a gas diffusion conductive layer 5.
- Such electrodes 2 and 3 are catalysts used in conventional solid polymer fuel cells. An electrode composed of a layer and a gas diffusion conductive layer can be suitably used, and detailed description of its structure and manufacturing method is omitted.
- Both electrodes 2 and 3 are disposed on both sides of the electrolyte layer 6 with the catalyst layers 4 and 4 facing inward.
- the electrolyte layer 6 and the surfaces of both electrodes 2 and 3 are in close contact with each other, and the power generation body 1 is a solid in the form of a membrane in which the electrolyte layer 6 and both electrodes 2 and 3 are integrated. It is easy to handle. For this reason, the unit battery 41 can be easily configured.
- FIG. 10 shows a unit battery 41 constituted by the power generation body 1 of this embodiment.
- the power generation body 1 is sandwiched between the separators 44a and 44b in which the gas flow channel 52 is formed, and the gas diffusion conductive layer 5 side of both the electrodes 2 and 3 is the separator It is brought into contact with the gas flow channel groove 52 of 44a, 44b.
- an annular spacer 45 is interposed between the separators 44a and 44b around the power generation body 1, and the thickness between the separators 44a and 44b is maintained at a constant width.
- the electrolyte layer 6 and the electrodes 2 and 3 are in close contact with each other to form an integral solid, so that a unit cell is manufactured as in the conventional power generation body.
- a fuel cell can be configured by stacking a plurality of such unit cells 41.
- the proton conductor 7 constituting the electrolyte layer 6 has excellent proton conductivity and can be manufactured at a very low cost as compared with ion exchange polymer membranes such as naphth ions. This makes it possible to manufacture a fuel cell having a low cost and a high electromotive force.
- a dry mixed powder of calcium carbonate and orthophosphoric acid is prepared to have an ol% composition. Then, the dry mixed powder is subjected to heat treatment at 1300 ° C. for 0.5 hour in an electric furnace to melt it. The melt is then poured onto a carbon plate and quenched to room temperature to obtain a calcium phosphate glass. By using this calcium phosphate glass, the diameter of the particles is 10 ⁇ m or less. Powder until bottom. Then, the obtained glass powder is put in a plastic petri dish, stirred with an equal weight of distilled water and stirred, and then left for about 3 days in a state of covering with lid to prevent drying, it is fluid and has high viscosity. A proton conducting gel can be obtained.
- the mold 10 includes a lower mold 11 having a molding recess 20 and a support surface 21 on the upper surface, and an upper mold 12 having a pressure surface 30 in pressure contact with the support surface 21 of the lower mold 11 on the lower surface.
- the lower mold 11 and the upper mold 12 are formed of thick stainless steel plates formed so as to form mutually congruent squares in plan view. Further, as shown in FIGS. 2, 4 and 5, two positioning holes 24 and 33 in the vertical direction are formed at the same position around the molds 11 and 12, respectively, and the positioning holes 24 and 33 are used for positioning 14 and 14 are inserted in a close fitting manner, and the upper mold 12 is slidably held along the positioning rods 14 and 14, and the pressing surface 30 of the upper mold 12 is supported by the support surface 21 of the lower mold 11. It is possible to move up and down to a position to overlap and a position to retract above the support surface 21.
- the molding recess 20 provided at the center of the upper surface of the lower mold 11 has a shallowly recessed square shape.
- the pressing surface 30 overlaps from above with the two molds 11 and 12 in an overlapping state, and the closing cavity 13 for molding the power generation body 1 inside the molding recess 20.
- the thickness of the power generator 1 is defined by the depth of the molding recess 20.
- a sliding hole 22 in the vertical direction communicating with the molding recess is formed at the bottom of the molding recess 20, and the pusher 23 shaped to be closely fitted to the slide hole 22 is a sliding hole. Slideably fit inside along 22.
- the pusher 23 has its upper surface flush with the bottom surface of the molding recess 20, and the lower molding position 1 for closing the opening of the slide hole 22 formed on the bottom surface of the molding recess 20 (see FIG. 6).
- the pressing surface 30 of the upper mold 12 has a square portion overlapping the molding recess 20 of the upper mold 12 in the overlapping state with the support surface 21 of the lower mold 11 as the molding surface 32.
- steps of molding the power generation body 1 using the mold 10 and curing the electrolyte layer 6 will be sequentially described according to FIGS.
- the fuel electrode 2 is mounted in the molding recess 20 of the lower mold 11 holding the extruder 23 at the molding position I, with its catalyst layer 4 facing upward.
- the electrode to be attached here may be an air electrode side electrode 3 instead of the fuel electrode side electrode 2 which is used on either one of the pair of electrodes 2 and 3, instead of the fuel electrode side electrode 2, .
- both electrodes 2 and 3 are cut in advance into a planar shape closely fitted to the forming recess 20.
- the above-described proton conductor 7 is disposed on the entire surface of the fuel electrode 2 attached to the molding recess 20.
- the amount of the proton conductor 7 is too small, a gap is generated between the air electrode 3 and the electrolyte layer 6 when the electrolyte layer 6 is formed, and therefore, the extent to which the entire area of the forming recess 20 is reached.
- Supply the proton conductor 7 (see Fig. 6 (b)).
- the air electrode 3 on the other side is placed above the proton conductor 7 disposed on the fuel electrode 2 with the catalyst layer 4 side facing downward.
- the proton conductor 7 is placed between the two electrodes 2 and 3 with the catalyst layer 4 facing inward. In such a state, it is considered that the proton conductor 7 slightly infiltrates into the voids of the surfaces of the electrodes 2 and 3.
- the proton conductor 7 By thus arranging the proton conductor 7 between the electrodes 2 and 3 and sandwiching pressure from the gas diffusion conductive layer side, by forming an electrolyte layer of a predetermined width between the catalyst layers, the electrodes 2 and 3 and The membrane-shaped power generation body 1 in which the proton conductor 7 is physically joined is formed.
- the electrolyte layer 6 of the power generation body 1 thus formed has sufficient proton conductivity.
- the force S and the flexibility of the proton conductor 7 make the power generation body 1 in a mechanically unstable state. Since it is difficult to handle, it is then held in the mold 10 and subjected to a heat treatment step to cure the proton conductor 7 into a solid state in a short period of time.
- the power generation body 1 immediately after being molded is left in the mold 10 and left for 6 hours under the conditions of 90 ° C. and 100% RH.
- the precipitation of phosphoric acid hydrate crystals in the proton conductor 7 is promoted to harden the proton conductor 7 into a solid state in a short time.
- the precipitation of calcium phosphate hydrate crystal which is strong proceeds gradually even at room temperature, it is possible to make the proton conductor 7 solid by leaving it to stand at room temperature for a long time (for example, 30 days).
- the power generation body 1 is in the form of a thin plate in which the electrolyte layer 6 and the electrodes 2 and 3 are integrated, and the handling is extremely easy.
- the step of depositing calcium phosphate hydrate crystals is performed under higher temperature conditions (for example, 90 ° C.), the deposition of crystals is promoted to make the electrolyte layer 6 solid in a short period of time. it can.
- the electrolyte layer 6 is cured, and the power generation body 1 integrated is displaced by displacing the pusher 23 of the lower mold 11 to the upper take-out position II, It is pushed up from below and taken out of the molding recess 20.
- the power generation body 1 fitted into the molding recess 20 can be easily removed without deformation.
- the power generation body 1 of the present invention can be variously modified without departing from the scope of the present invention, which is not limited to the above-described embodiment.
- zinc phosphate and magnesium phosphate are used as the phosphate using calcium phosphate as the phosphate constituting the phosphate molecular chain of the proton conductive gel.
- a proton conductive gel can be produced by the same method as this example, and the proton conductive gel can be used as an electrolyte layer of a fuel cell power generator.
- the proton conductor is not limited to a complex in which phosphate hydrate crystals are precipitated in a proton conducting gel consisting of a phosphate molecular chain and water as in this example, but other proton conducting substances may be used. It is also possible to use a mixture of them.
- the power generation body 1 is formed in a square planar shape by matching the outer edges of the electrolyte layer 6 and the electrodes 2 and 3 in accordance with the shape of the closed cavity 13 of the mold 10. The outer edges of the electrode 6 and the electrodes 2 and 3 do not have to coincide with each other in the vertical direction, and the planar shapes thereof can be changed as appropriate.
- the fuel cell 40 mainly includes a stack 48 in which thin plate-like unit cells 41 are stacked and connected in series.
- the unit battery 41 is configured by sandwiching the power generation body 1 with a pair of separators 44a and 44b.
- a plurality of manifolds 46 and 46 passing through each unit cell 41 are formed in the stack 48 in the vertical direction, and hydrogen, which is a fuel gas, and air, are each unit cell via the manifolds 46.
- the fuel cell 40 of the present embodiment is equipped with a gas supply device for supplying gas to the manifold 46, a current collector, a cooling device (not shown), etc.
- the same configuration as the molecular fuel cell can be suitably used, and the description thereof is omitted.
- the unit battery 41 will be described in more detail with reference to FIGS.
- the unit cell 41 has a generator contact portion 50 provided with a gas flow passage groove 52 and a power generator 1 generating a potential difference between the fuel electrode 2 and the air electrode 3 by the reaction of hydrogen and oxygen.
- a pair of fuel electrode side separators 44a and an air electrode side separator 44b sandwiching the power generation body 1 and an annular spacer 45 interposed between the separators 44a and 44b around the power generation body 1.
- Positioning holes 47 and 47 in the vertical direction are formed on the outer peripheral portion of the unit cell 41, and the positioning holes 47 are externally fitted to the positioning rod 49, thereby laminating a plurality of unit cells 41 vertically.
- Configure stack 48 (see Figure 8). Further, as shown in FIG.
- the manifolds 46, 46 penetrating the outer peripheral portion of the unit cell 41 up and down communicate with the gas flow channel 52, respectively, and from the manifold 46 for supply to the gas flow channel. Hydrogen or air is supplied to the generator 1 through the groove 52, and the reacted gas is discharged from the discharge manifold 46. Also, between the encapsulation formed between the outer edge of the power generation body 1 and the inner edge of the annular spacer 45 The space 56 is filled with a sealing agent 57 consisting of silicone grease.
- the unit cell 41 of the present embodiment has a vertically symmetrical shape, and the configurations of the separators 44a and 44b and the electrodes 2 and 3 have the same configuration on both sides of the fuel electrode and the air electrode. There is no problem even if the configuration of the two poles is asymmetrical according to the characteristics of.
- the fuel electrode side separator 44a and the air electrode side separator 44b sandwiching the power generation body 1 are manufactured by cutting a hydrogen impermeable carbon plate. As described above, since both the separators 44a and 44b have the same shape, only the separator 44a on one side is shown in FIG. 11 and explained. It is divided into a central generator contact portion 50 in contact and a spacer support portion 51 around the generator contact portion 50 in pressure contact with the annular spacer 45. Then, a serpentine gas passage groove 52 is formed in the generator contact portion 50, and the through holes 53 a in the vertical direction constituting the manifold 46 and the positioning hole 47 are formed in the spacer support portion 51. , 53b are formed.
- both ends of the gas flow channel 52 are in communication with the through holes 53 a and 53 a of the spacer support portion 51 forming the manifold 46. Further, the portion of the gas flow passage groove 52 which straddles the boundary between the power generation body contact portion 50 and the spacer support portion 51 is a portion which comes in contact with the sealing gap 56 filled with the sealing agent 57.
- a cover 59 made of carbon is attached to the formed recess 58 to cover the gas flow channel 52 from above, and when assembling the unit battery 41, the excess flow of sealing agent 57 causes the gas flow channel 52 to Prevent blocking.
- the separator of the present invention is not limited to the shape of the present embodiment, and the gas flow channel 52 and other shapes may be changed on the fuel electrode side and the air electrode side, and each separator is an adjacent unit cell 41 It may be integrally molded with the separator. Also, as a material of the separator, stainless steel or the like can be used instead of carbon.
- the annular spacer 45 is formed by cutting a plate-like Teflon, and as shown in FIG. 12, it has a rectangular frame shape having a square inner circumferential area 62 in which the power generation body 1 is fitted in the center. Form . Then, the annular spacer 45 is formed slightly thinner than the thickness of the power generation body 1 (for example, 0.1 m m), and when the power generation body 1 is sandwiched between the separators 44a and 44b, the separators 44a and 44b and When the power generating body 1 is compressed in the width direction, the annular spacer 45 supports between the power generating body abutting portions 50 of the separators 44a and 44b, and the power generating body 1 is compressed. Excessive pressure Prevent this.
- inward supporting supporting protrusions 61, 31 are disposed, and the supporting protrusions 61 are provided on the outer edge of the power generation body 1 fitted in the inner circumferential area 62.
- the generator 1 is supported from four directions, and an enclosed gap 56 for filling the sealing agent 57 is formed between the outer edge of the generator 1 and the inner edge of the annular spacer 45.
- through holes 55a constituting the manifold 46 at the time of assembling the unit cell 41 and through holes 55b constituting the positioning hole 47 are formed at appropriate positions on the upper and lower surfaces of the annular spacer 45.
- the integral thin plate-like power generation body 1 is placed on the power generation body contact portion 50 of the separator 44 a on one side, and the power generation body 1 is annularly Fit the spacer 45 on the outside. Then, the sealing gap 57 formed between the annular spacer 45 and the power generation body 1 is filled with the sealing agent 57 of silicon grease to prevent gas leakage through the outer edge of the power generation body 1, and the opposite side
- the unit cell 41 is manufactured by stacking the separators 44b from the top from the top and sandwiching the power generation body 1 between the power generation body contact portions 50 of the both separators 44a and 44b.
- both separators 44a and 44b are held with a certain amount of force or more, the power generation body 1 is compressed, and the hard annular spacer 45 supports the separators 44a and 44b outside the power generation body 1 And define the width between the separators 44a and 44b so that no pressure exceeding a predetermined amount is applied to the power generation body 1.
- the membrane-like electrolyte layer 6 closely bonds the proton conductor 7 mainly composed of the proton conductive gel to the electrodes 2 and 3. Because it is used as an energy source, it is possible to realize high and stable power generation efficiency. In addition, the material cost of this proton conductor 7 is extremely inexpensive compared to naphthic ions, and a unit cell 41 using proton conductor 7 for electrolyte layer 6 can be manufactured by the above simple manufacturing method.
- the fuel cell 40 of the present embodiment is suitable for mass production at a low manufacturing cost.
- the fuel cell 40 of the present invention can be variously modified without departing from the scope of the present invention, which is not limited to the above-described embodiment.
- the generator contact portion 50 of the separators 44a and 44b and the spacer support portion 51 are formed on the same surface, they have a difference in height between them. It doesn't matter if it is something.
- various known configurations can be used as appropriate for the lamination mechanism of the unit battery 41, the shape of the manifold 46, the cooling mechanism, and the like.
- FIG. 1 is a longitudinal side view of a power generation body 1 according to an embodiment of the present invention.
- FIG. 2 is a perspective view of a mold 10
- FIG. 3 It is a central longitudinal side view of the forming die 10.
- FIG. 4 A top view of the lower mold 11.
- FIG. 5 is a bottom view of the upper mold 12
- FIG. 6 is an explanatory view (a), (b) and (c) showing a molding process of the power generation body 1.
- FIG. 8 is an enlarged front view of a fuel cell 40 showing a stacking mode of unit cells 41.
- FIG. 9 is an exploded perspective view of a unit battery 41.
- FIG. 10 It is a central longitudinal side view of a unit battery 41.
- FIG. 11 is a plan view of a separator 44a.
- FIG. 12 is a plan view of an annular spacer 45.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005506474A JPWO2004107487A1 (ja) | 2003-05-30 | 2004-05-24 | 燃料電池用発電体、該燃料電池用発電体の製造方法、該燃料電池用発電体の製造に用いる成形型及び該燃料電池用発電体を用いた燃料電池 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003-153820 | 2003-05-30 | ||
JP2003-153839 | 2003-05-30 | ||
JP2003153839 | 2003-05-30 | ||
JP2003153820 | 2003-05-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004107487A1 true WO2004107487A1 (ja) | 2004-12-09 |
Family
ID=33492445
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/007076 WO2004107487A1 (ja) | 2003-05-30 | 2004-05-24 | 燃料電池用発電体、該燃料電池用発電体の製造方法、該燃料電池用発電体の製造に用いる成形型及び該燃料電池用発電体を用いた燃料電池 |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPWO2004107487A1 (ja) |
WO (1) | WO2004107487A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007265803A (ja) * | 2006-03-28 | 2007-10-11 | National Institute Of Advanced Industrial & Technology | プロトン伝導性結晶化ガラス固体電解質 |
JP2010517754A (ja) * | 2007-02-09 | 2010-05-27 | ソルヴェイ(ソシエテ アノニム) | 重金属で汚染された物質の処理方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002015751A (ja) * | 2000-06-30 | 2002-01-18 | Aisin Takaoka Ltd | 燃料電池及びそのセパレータ |
JP2002042836A (ja) * | 2000-07-19 | 2002-02-08 | Honda Motor Co Ltd | 燃料電池用シールおよびその成形方法 |
WO2002019454A1 (fr) * | 2000-08-30 | 2002-03-07 | Sanyo Electric Co., Ltd. | Unite de cellule electrochimique et son procede de fabrication |
JP2003109622A (ja) * | 2001-07-26 | 2003-04-11 | Matsushita Electric Ind Co Ltd | 燃料電池セパレータとその製造方法および燃料電池 |
JP2003217339A (ja) * | 2002-01-16 | 2003-07-31 | Nagoya Industrial Science Research Inst | プロトン伝導ゲル、プロトン伝導体及びこれらの製造方法 |
-
2004
- 2004-05-24 WO PCT/JP2004/007076 patent/WO2004107487A1/ja active Application Filing
- 2004-05-24 JP JP2005506474A patent/JPWO2004107487A1/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002015751A (ja) * | 2000-06-30 | 2002-01-18 | Aisin Takaoka Ltd | 燃料電池及びそのセパレータ |
JP2002042836A (ja) * | 2000-07-19 | 2002-02-08 | Honda Motor Co Ltd | 燃料電池用シールおよびその成形方法 |
WO2002019454A1 (fr) * | 2000-08-30 | 2002-03-07 | Sanyo Electric Co., Ltd. | Unite de cellule electrochimique et son procede de fabrication |
JP2003109622A (ja) * | 2001-07-26 | 2003-04-11 | Matsushita Electric Ind Co Ltd | 燃料電池セパレータとその製造方法および燃料電池 |
JP2003217339A (ja) * | 2002-01-16 | 2003-07-31 | Nagoya Industrial Science Research Inst | プロトン伝導ゲル、プロトン伝導体及びこれらの製造方法 |
Non-Patent Citations (2)
Title |
---|
KASUGA TOSHIHIRO ET AL.: "Fast Proton Conductors Derived from Calcium Phosphate Hydrogels", ADVANCED MATERIALS, vol. 14, no. 20, 2002, pages 1490 - 1492, XP001130271 * |
KASUGA TOSHIHIRO ET AL.: "Rinsan'en Glass no Hydeo-gel-ka o Riyo shita Ko-Proton Dendo Zairyo no Sakusei", JOURNAL OF THE SOCIETY OF INOEGANIC MATERIALS, vol. 10, 2003, pages 189 - 193, XP002983084 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007265803A (ja) * | 2006-03-28 | 2007-10-11 | National Institute Of Advanced Industrial & Technology | プロトン伝導性結晶化ガラス固体電解質 |
JP2010517754A (ja) * | 2007-02-09 | 2010-05-27 | ソルヴェイ(ソシエテ アノニム) | 重金属で汚染された物質の処理方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2004107487A1 (ja) | 2006-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2464112C (en) | One-shot fabrication of membrane-based electrochemical cell stacks | |
CA2506592C (en) | Membrane electrode assembly with periphery gasket and sealing channels | |
US6946210B2 (en) | Electrochemical polymer electrolyte membrane cell stacks and manufacturing methods thereof | |
CN102956900B (zh) | 成形和填充子衬垫 | |
CN108346810B (zh) | 燃料电池微型密封件及其制造方法 | |
US20070087253A1 (en) | Method of manufacturing a fuel cell array and a related array | |
US20150228988A1 (en) | Membrane electrode assembly, fuel cell comprising assembly of this type and motor vehicle comprising said fuel cell | |
CN107534166B (zh) | 用于固体聚合物电解质燃料电池的密封件 | |
JP4585310B2 (ja) | 膜式電気化学的電池スタック | |
EP1573846A2 (en) | Liquid electrochemical cell stacks and manufacturing methods for same | |
CN102057527B (zh) | 燃料电池和燃料电池的制造方法 | |
US7681304B2 (en) | Membrane electrode assembly and method of manufacturing a membrane electrode assembly | |
WO2004107487A1 (ja) | 燃料電池用発電体、該燃料電池用発電体の製造方法、該燃料電池用発電体の製造に用いる成形型及び該燃料電池用発電体を用いた燃料電池 | |
JPH0878028A (ja) | 固体高分子電解質燃料電池およびその製造方法 | |
JP2005011624A (ja) | 固体高分子型燃料電池用セル部材およびその製造方法 | |
CN1553532A (zh) | 一种高效燃料电池导流双极板及其制造方法 | |
CN101689654B (zh) | 用于平板式燃料电池的不透性多孔基板及一体化封装体 | |
WO2005078837A1 (ja) | 燃料電池 | |
CN107742735B (zh) | 一种mea包胶的密封结构及其制造方法和使用方法 | |
JP2006164642A (ja) | 燃料電池 | |
KR101027098B1 (ko) | 연료 전지 및 그 제조 방법 | |
JP2005032481A (ja) | 燃料電池に用いる単位電池、及び該単位電池の製造方法 | |
JP2010192391A (ja) | 燃料電池用多孔膜複合体、燃料電池用電解質膜−電極−多孔膜複合体、及びこれらの製造方法 | |
WO2022260829A9 (en) | Nafion self-bonding for cost-effective rapid assembly of a thin flexible fuel cell by a template-based thermal sealing process | |
CN1787265A (zh) | 可重装的微型自吸氧式直接甲醇燃料电池及其封装方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005506474 Country of ref document: JP |
|
122 | Ep: pct application non-entry in european phase |