WO2003088395A1 - Pile a combustible a electrolyte polymerique - Google Patents
Pile a combustible a electrolyte polymerique Download PDFInfo
- Publication number
- WO2003088395A1 WO2003088395A1 PCT/JP2003/004723 JP0304723W WO03088395A1 WO 2003088395 A1 WO2003088395 A1 WO 2003088395A1 JP 0304723 W JP0304723 W JP 0304723W WO 03088395 A1 WO03088395 A1 WO 03088395A1
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- WIPO (PCT)
- Prior art keywords
- current collector
- polymer electrolyte
- plate
- fuel cell
- gas
- Prior art date
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Classifications
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- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- 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
-
- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
-
- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0267—Collectors; Separators, e.g. bipolar separators; Interconnectors having heating or cooling means, e.g. heaters or coolant flow channels
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
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- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
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- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
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- 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
- the present invention relates to a fuel cell used for a portable power supply, a power supply for an electric vehicle, a cogeneration system and the like, and particularly to a current collector plate of a polymer electrolyte fuel cell.
- a solid polymer electrolyte fuel cell electrochemically transfers a fuel gas containing hydrogen and an oxidizing gas containing oxygen, such as air, through a polymer electrolyte membrane that selectively transports hydrogen ions. It reacts to generate electric power.
- This fuel cell usually has a plurality of unit cells each consisting of an anode and a cathode sandwiching a polymer electrolyte membrane, an anode separator for supplying a fuel gas to the anode, and a cathode separator supplying an oxidant gas to a cathode. It is composed of a stacked cell stack. At both ends of the cell stack, an end plate is overlapped with a current collecting plate for taking out current and an insulating plate for electrically insulating the outside from the outside, and both end plates are fastened by fastening means. Appropriate fastening pressure is applied. The end plate is provided with means for the supply and discharge of fuel gas, oxidant gas and coolant. In this way, a unit called a fuel cell stack is formed.
- the current collector plates In order to supply the fuel gas, the oxidizing gas, and the coolant to the cell stack, at least one of the current collector plates located at both ends is provided with a through hole for flowing the gas or coolant. In order to prevent corrosion of this through-hole, and to reduce the contact resistance between adjacent cells and separators, the current collector plate is usually used by plating a metal material such as stainless steel or copper with gold. . In the case of gold-plated current collectors, if the thickness of the gold plating is insufficient, the base point is a minute pit, and eventually corrosion will progress. For this reason, anti-corrosion structures have been proposed to prevent gas from coming into direct contact with through holes for supplying and discharging gas and coolant.
- a gold-plated metal current collector has the following problems.
- the water content of the polymer electrolyte membrane must be high, so the supply gas and exhaust gas contain a large amount of water vapor.
- metal current collector plates are susceptible to corrosion in areas where supply gas and exhaust gas come into contact. If metal corrosion occurs in the gas supply path, the performance of the electrolyte membrane will be reduced because the generated metal ions will be mixed.
- the insulation of the coolant decreases, and the generated power decreases due to leakage current.
- the present invention provides a polymer electrolyte fuel cell including an improved current collector plate, the fuel cell comprising: a hydrogen ion conductive polymer electrolyte membrane; an anode sandwiching the polymer electrolyte membrane; A plurality of unit cells consisting of an anode separator having a gas flow path for supplying fuel gas to the anode and a cathode separator having a gas flow path for supplying oxidizing gas to the cathode were stacked. It comprises a cell stack, a pair of current collectors sandwiching the cell stack, and a pair of end plates for fastening the cell stack and the current collector in a pressurized state.
- the current collector plate according to the present invention is composed of a conductive carbon material as a main component, and a terminal for connecting a current extraction cable is provided near a fuel gas or oxidant gas inlet side manifold.
- the terminal portion has a coating layer of a good electric conductor.
- the coating layer of the electric conductor is provided in a region extending from the terminal portion to a portion corresponding to the gas flow path inlet side of the cell, which is connected to the inlet side manifold.
- FIG. 1 is a partially sectional side view showing an example of the structure of a fuel cell stack according to the present invention.
- FIG. 2 is a front view of the current collector plate according to Embodiment 1 of the present invention.
- Figure 3 is a rear view of the same current collector.
- FIG. 4 is a cross-sectional view taken along the line IV-IV of FIG.
- FIG. 5 is a perspective view of a main part showing another example of connection of a cable to a current collector plate.
- FIG. 6 is a front view of the current collector plate according to Embodiment 2 of the present invention.
- FIG. 7 is a rear view showing another example of the current collector plate.
- FIG. 8 is a front view showing an example of an insulating plate used in combination with the current collecting plate.
- FIG. 9 is a front view of the separator on the anode side according to Embodiment 3 of the present invention. It is.
- FIG. 10 is a front view of a current collector combined with the separator plate of FIG. 9.
- FIG. 11 is a sectional view taken along line XI-XI of FIG.
- FIG. 12 is a front view of the cathode-side separator according to the third embodiment of the present invention.
- Fig. 13 is a front view of the current collector combined with the separator plate of Fig. 12.
- FIG. 14 is a cross-sectional view taken along line XIV-XIV in FIG.
- FIG. 15 is a front view showing another anode side separator.
- FIG. 16 is a front view of a current collector combined with the separator of FIG. 15, and FIG. 17 is a front view showing another cathode-side separator.
- FIG. 18 is a front view of a current collector combined with the separator of FIG. 17, and FIG. 19 is a longitudinal sectional view showing another example of the current collector.
- FIG. 20 is a front view of an anode-side current collector plate according to Embodiment 4 of the present invention.
- FIG. 21 is a front view of a cathode-side current collector according to Embodiment 4 of the present invention.
- FIG. 22 is a front view of the anode-side current collector plate according to the fifth embodiment of the present invention.
- FIG. 23 is a rear view of the anode side current collector of FIG.
- FIG. 24 is a front view of the anode-side current collector plate according to the sixth embodiment of the present invention.
- FIG. 25 is a sectional view taken along line XXV-XXV of FIG.
- FIG. 26 is an enlarged sectional view of a main part showing an example in which an electric conductor layer is formed on the surface of a core metal plate.
- the present inventors have studied to use a plate material or a formed plate mainly composed of a carbon material having no possibility of corrosion as a current collector. As a result, it was found that an effect peculiar to a polymer electrolyte fuel cell can be obtained by providing the current extraction terminal of the current collector plate near the manifold on the inlet side of the reaction gas, especially the fuel gas. . That is, the electrode is humidified by the water generated by the reaction on the inlet side of the reaction gas supplied thereto. Further, the polymer electrolyte membrane that exhibits hydrogen ion conductivity in a state containing water can be efficiently humidified.
- the terminal portion is provided in the vicinity of the inlet gas-side manifold of the current collector plate, and the current density in the electrode reaction portion close to the inlet-side manifold is increased. As a result, the amount of water generated by the reaction increases, and the electrode can be kept highly humidified.
- a current collector plate made of a conductive graphite plate or a molded plate made of a composite material of a conductive carbon material and a binder is electrically anisotropic so that the electrical resistivity in the surface direction is reduced as described later.
- its electrical resistivity is higher than that of a metal current collector. Therefore, in the plane of the current collector plate, the electric resistance between the terminal portion and the terminal portion is smaller in a portion near the terminal portion than in a portion far from the terminal portion. For this reason, there is a difference in current density between a portion near and far from the terminal portion, and the former having a higher current density increases the amount of electrode reaction.
- the durability of the electrode can be improved by increasing the humidification of the reaction gas inlet, in particular, the vicinity of the fuel gas inlet, where humidification by the generated water at the electrode is not expected. Also, the humidification amount of the fuel gas supplied to the battery can be reduced, and the energy efficiency can be improved.
- the current extraction terminal portion of the current collector plate has a coating layer made of a metal film or plate that is a good electrical conductor.
- a coating layer made of a metal film or plate that is a good electrical conductor.
- the present inventors have also studied to use a current collector plate whose electric resistivity in the surface direction is smaller than the electric resistivity in the thickness direction, that is, in the stacking direction of the hooks.
- a current collector plate whose electric resistivity in the surface direction is smaller than the electric resistivity in the thickness direction, that is, in the stacking direction of the hooks.
- the current collector is integrated with the separator in contact with the current collector.
- the terminals of the current collector plate are The metal plate that connects the cable that extracts the force is fastened at two or more points. This can prevent the terminal portion of the current collector from cracking.
- the current collector plate containing conductive carbon as a main component used in the present invention is obtained by processing a conductive carbon plate such as a commercially available glassy carbon plate or expanded graphite plate into a predetermined shape by cutting or blasting. Is suitable.
- a conductive carbon plate such as a commercially available glassy carbon plate or expanded graphite plate into a predetermined shape by cutting or blasting.
- the conductive carbon plate one having an electric resistivity in the plane direction of about 1 ⁇ ⁇ cm or less is preferably used.
- a more preferable current collector plate is a thermoplastic resin such as polyphenylene sulfide or polypropylene, or a thermosetting resin such as an epoxy resin or a phenol resin, or a mixture thereof to which a molding material obtained by adding graphite powder is used.
- the thickness of the current collector plate may be changed between the terminal portion and other portions.
- the thickness of the current collector plate must be a value that does not destroy it, at least about 3 to 6 mm.
- Embodiment 1 Embodiment 1
- FIG. 1 shows an example of a polymer electrolyte fuel cell stack according to the present embodiment.
- the electrolyte membrane electrode assembly (MEA) denoted by 1 comprises a polymer electrolyte membrane, an anode sandwiching the polymer electrolyte membrane, and a force sword.
- the polymer electrolyte membrane has a size one size larger than the electrode.
- the periphery of the polymer electrolyte membrane is sandwiched between gaskets.
- This MEA 1 is alternately stacked with separations.
- the separator has a flow path for oxidant gas on one side and a flow path for fuel gas on the other side.
- a single separator that serves as both a source side separator and an anode side separator.
- the laminate of t the cell forces cathode side separator Isseki and the anode side separator Isseki two kinds of composite separator evening 2 a in which a flow path of the click one plant between both is used
- the upper end of the stack has an end plate 5a via a current collector plate 3a on the power source side and an insulating plate 4a, and the lower end of the laminate has a current collector plate 3b and an insulating plate 4b on the anode side.
- the end plates 5a and 5b, on which the end plates 5b are overlapped, are fastened by bolts 6 and nuts 8, and a predetermined load is applied to the cell laminate. 7 represents a spring.
- the end plate 5a is provided with entrances and exits for the reaction gas and the coolant.
- an oxidizing gas outlet 11, a fuel gas inlet 12 and a coolant outlet 13 are shown.
- the polymer electrolyte fuel cell battery pack 10 is assembled.
- the current collectors 3a and 3b have their terminals 15a and 15b projecting from the side of the cell stack, and the terminals 16a and 16b They are connected by brackets 15a and 15b, respectively.
- the current collectors 3 a and 3 b are shown as also serving as the power source separator and the anode separator, respectively. It is not limited to.
- FIG. 3 is a front view of the current collector plate on the force sword side
- FIG. 3 is a rear view thereof
- FIG. 4 is a cross-sectional view taken along line IV-IV of FIG.
- the power extraction cable and the metal plate to connect it are omitted.
- the current collector 30 has a pair of oxidant gas manifold holes 31, a fuel gas manifold hole 32, and a coolant manifold hole 33.
- the current collector plate 30 has a flow path 34 for an oxidizing gas communicating with the pair of manifold holes 31 on a surface facing the force sword.
- the current collector plate 30 has grooves 37, 38, and 39 for mounting O-rings surrounding the manifold holes 31, 32, and 33 on the surface facing the insulating plate. O-rings fitted in these grooves are compressed between the current collector plate and the insulating plate to prevent gas and coolant from leaking from each manifold hole.
- the current collecting plate 30 further has a terminal portion 35 having two holes 36, and two metal plates 45 sandwiching the terminal portion 35 are provided on the terminal portion with screws 46 and nuts 47. Is attached.
- Reference numeral 48 denotes a spring washer, and reference numeral 49 denotes a flat washer.
- a core wire 41 of a power extraction cable 40 is connected to the metal plate 45 by soldering 42.
- the pair of oxidizing gas manifold holes 31 and the fuel gas manifold holes 32 the one closer to the terminal portion 35 is the inlet side.
- connection point between the terminal portion 35 of the current collector 30 and the metal plate 45 for connecting the power extraction cable is not particularly limited, but as shown in FIG. 2 and FIG. Or more. This is because the loss due to resistance is reduced by making the contact pressure uniform, and the stress generated by fastening is easily leveled.
- a metal plate can be connected to only one side in addition to connecting a metal plate to both sides of the terminal portion.
- connecting metal plates on both sides has the effect of increasing the contact surface and reducing the contact resistance.
- the response The force is equalized, and the effect of preventing breakage due to excessive tightening force can be obtained.
- FIG. 5 shows another example in which a power extraction cable 40 is connected to the terminal portion 35 of the current collector 30.
- the terminal portion 35 of the current collector plate 30 is fitted to a U-shaped connection bracket 43 to which the cable 40 is soldered, and both are fixed by screws 44 passing through the hole 36.
- the fastening means including the port, the spring, and the nut is used for fastening the fuel cell stack, but may be changed to another fastening means.
- a hole was made in the terminal to connect the power extraction cable to the terminal of the current collector, and a metal plate was connected with screws and nuts.
- other connection methods can be used.
- a screw hole may be formed in the terminal portion 35, and a crimp terminal to which a power cable is connected may be connected to the hole by screwing.
- Another connection method that can stably maintain the electrical connection may be adopted.
- the power extraction cable and the metal plate connecting the cable were connected by soldering, but any method that can maintain good electrical connection such as crimping by crimping may be used.
- a metal material having low contact resistance may be used.
- metals such as bronze and copper having low electric resistance and good workability can be used.
- FIG. 6 is a front view of the current collector plate on the cathode side in the present embodiment.
- the current collector plate 3OA has a metal film 50 with a thickness of about 1 m on both sides of the terminal portion 35.
- Other configurations are the same as those of the current collector 30 shown in FIG. With this metal film 50, the contact resistance between the terminal portion 35 of the current collector plate and the metal plate or the like connecting the power extraction cable can be reduced.
- FIG. 7 shows still another example of the current collector plate.
- a metal film 51 having a thickness of several meters to several tens // m is formed on substantially the entire surface facing the insulating plate.
- the in-plane conductivity of the current collector plate can be improved, and the resistance loss can be further reduced.
- no metal film is formed up to a position slightly away from the grooves 37, 38, and 39 for mounting the O-rings surrounding each manifold hole.
- a metal forming the metal film a material that can impart conductivity may be used other than copper or aluminum.
- vapor deposition or thermal spraying can be used, but thermal spraying is preferable because a predetermined thick film can be formed in a short time.
- Other structures are the same as in the first embodiment.
- FIG. 8 shows an insulating plate installed on the back of the current collector plate of FIG. 2 or FIG.
- the insulating plate 60 has a pair of manifold holes 61 for oxidizing gas, a manifold hole 62 for fuel gas, and a manifold hole 63 for coolant, respectively.
- FIG. 9 is a front view of the anode-side separator
- FIG. 10 is a front view of the current collector plate in contact with the anode-side separator
- Fig. 12 is a front view of the separator on the cathode side
- Fig. 13 is a front view of the current collector in contact with the separator on the cathode side.
- the separator 110 on the anode side has a pair of manifold holes 1 1 1 for oxidizing gas, a manifold hole 1 1 2 for fuel gas, and a manifold hole 1 1 3 for coolant.
- a pair of manifolds on opposing surfaces It has a fuel gas flow path 1 16 communicating with the hole 1 1 2.
- the current collectors 120 arranged on the back of the separator 110 have a pair of oxidant gas manifold holes 121, a fuel gas manifold hole 122, and a coolant manifold. Hold holes 1 2 3 are provided.
- the current collector plate 120 is connected to the terminal part 125 by the inlet side manifold hole of the fuel gas manifold hole of the separator 110 (as clearly shown by the arrow indicating the gas flow direction). In the figure, it is provided near the upper left manifold hole) so as to protrude outward.
- An electric conductor covering layer 127 is provided in this terminal part 125 and the part connected to it, that is, the area corresponding to the inlet side of the inlet side manifold hole and the gas flow path connected to it in front of the separator 120.
- An electric conductor covering layer 127 is provided in this terminal part 125 and the part connected to it, that is, the area corresponding to the inlet side of the inlet side manifold hole and the gas flow path connected to it in front of the separator 120.
- An electric conductor covering layer 127 is provided in this terminal part 125 and the part connected to it, that is, the area corresponding to the inlet side of the inlet side manifold hole and the gas flow path connected to it
- the cathode side separator 130 has a pair of manifold holes 13 1 for oxidant gas, a manifold hole 13 2 for fuel gas, and a manifold hole 13 3 for coolant.
- the oxidizing gas flow path 134 that communicates the pair of manifold holes 131 is provided on the surface opposite to.
- the current collectors 140 arranged on the back of the separator 130 have a pair of oxidant gas manifold holes 141, a fuel gas manifold hole 144 and a coolant manifold. It has two hold holes 1 4 3.
- the current collector plate 140 connects the terminal section 144 to the inlet-side manifold hole of the oxidizing gas manifold hole 130 of the separator 130 (the upper right manifold hole in the figure).
- the terminal portion 1 45 and a portion connected thereto that is, a region 1 4 6 corresponding to the inlet side manifold hole of the separator 130 and the inlet side of the gas flow path connected thereto are provided with an electric conductor.
- Coating layer 1 4 7 is provided.
- the region 146 has a thickness smaller than that of the other portions, and is provided with a coating layer 147 on both sides thereof so as to have the same thickness as the other portions.
- the terminal portion 145 has a hole 148 for attaching a metal plate for connection to a current extraction cable.
- the coating layer 1 27 of the terminal 1 2 5 of the current collector 1 20 corresponds to the inlet side of the gas flow path 1 16 in the separation plate 1 10 It extends to the part where it does. Since the coating layer 127 made of a metal film or a metal plate has lower electric resistance than the other parts mainly composed of the carbon material, when the current is taken out from the terminal part 125 during power generation, the current density is as described above. Higher in some areas. As a result, the cell electrode reaction proceeds preferentially on the inlet side of the gas flow path 116. Similarly, also on the force sword side, it proceeds preferentially on the inlet side of the gas flow channel 134.
- the amount of water generated by the reaction increases near the gas inlet side manifold hole, and the reaction gas supplied downstream is humidified.
- the terminals 1 25 of the anode-side current collector and the terminals 1 45 of the cathode-side current collector face each other, that is, the fuel gas inlet side. It is preferable to provide the manifold hole and the manifold hole on the inlet side of the oxidizing gas in close proximity.
- Figs. 15 to 18 show modified examples of the above combination of separator and current collector.
- the anode side separator 110A shown in Fig. 15 is the same as the separator 110 in Fig. 9 except that the position of the oxidant manifold hole 111A is changed.
- the current collector plate 120 A placed on the back of the separator 110 A has a different position of the oxidizer manifold hole 121 A and the shape of the coating layer 127 A Except for the difference, it is the same as the current collector 120 of FIG.
- the cathode side separator 130 A shown in Fig. 17 is Except that the position of the hold hole 13 1 A was changed, it is the same as the separator 130 in FIG.
- the current collector plate 140 A placed on the back of the separator 130 A has a different position of the oxidizing agent manifold hole 141 A and the shape of the coating layer 144 A Except for the difference, it is the same as the current collector plate 140 of FIG.
- the coating layers 127, 127 A, 147 and 147 A shown here can be formed by the metal film described in the second embodiment. However, in a more preferred embodiment, the coating layer is formed of a metal plate.
- the above-mentioned coating layer is formed of a metal plate, and a part of the coating layer enters the inside of the projected area of the separator laminated on the current collector plate as shown in FIG.
- the metal plate is loaded with the fastening load of the stack between the separator and the current collector plate. Then, the metal plate is firmly fixed according to the fastening load of the stack. Since the metal plate also covers the terminals of the current collector plate, it works to effectively reduce the stress applied to the base of the terminals by the cable connected to the terminals.
- the metal plate be fixed to the current collector plate with an elastic adhesive such as a conductive adhesive or a silicone adhesive.
- An insulating adhesive such as a silicone adhesive is interposed in a specific region between the current collector and the metal plate, and is useful for limiting the current density in a specific portion of the current collector.
- FIG. 19 shows an example in which a metal plate 127 is bonded to a current collector plate 120 part 126 with a conductive adhesive 122.
- the metal plate is fixed to the current collector plate with the adhesive as described above, the step between the current collector plate and the metal plate is eliminated, and it is more effective in reducing the stress at the terminal portion.
- a metal plate and a current collecting plate are bonded with a conductive adhesive, when collecting 3 OA of current at the terminal of the current collecting plate, the current collecting at both ends of the stack is compared with the case where no adhesive is used. It was confirmed that a voltage of about 5 mV was high between the plates.
- FIGS. 20 and 21 show the current collector plate in the present embodiment.
- FIG. 20 is a front view of the current collector plate on the node side.
- This current collector plate 120B has the same structure as the current collector plate of Fig. 10 except that the terminal portion 125B and the portion connected to it do not have the coating layer 127. It is located on the back of the 110-side separator shown.
- FIG. 21 is a front view of the current collector plate on the force sword side.
- the current collector plate 140B has the same structure as the current collector plate of FIG. 13 except that the terminal portion 144B and the portion connected to the current collector plate 144B do not have the coating layer 144. It is located on the back of the cathedral side separator shown below.
- Each of the current collector plates shown here is composed of a molded body of a carbon material and a composite material of a binder. Therefore, at the time of power generation, the current density becomes high near the terminal portion, that is, near the gas inlet side manifold hole, and the effect of humidifying the gas is exhibited as in the fourth embodiment.
- Embodiment 5
- Fig. 22 is a front view of the current collector plate which also serves as the separator on the anode side
- Fig. 23 is its rear view.
- the current collector 150 has a pair of oxidant gas manifold holes 151, a fuel gas manifold hole 152, and a coolant manifold hole 153.
- the fuel gas flow path 156 which communicates with the pair of manifold holes 152 is provided on the surface opposed to the fuel cell.
- the current collector plate 150 is the inlet-side manifold hole of the anode side manifold hole 152.
- the upper left manifold hole in Fig. 22 has a terminal part 155, and the backside has a coating layer extending to the vicinity of the manifold hole 155.
- FIG. 24 is a front view of the current collector plate of the present embodiment
- FIG. 25 is a cross-sectional view taken along line XXV-XXV of FIG.
- the current collector plate 160 is formed of a molding material composed of a conductive carbon material and a binder so as to surround the core metal plate.
- the current collector plate 160 has a pair of manifold holes 16 1 for oxidizing gas, a manifold hole 16 2 for fuel gas, and a manifold hole 16 3 for coolant. It has a terminal portion 1 65.
- the metal plate 166 embedded in this current collector has a smaller size than that of the current collector so that there is no part exposed to the outside, and the part corresponding to each manifold hole is Has holes larger in diameter than manifold holes.
- FIG. 26 shows an example in which an electric conductor layer 169 is formed on the surface of a core metal plate.
- this layer the contact resistance between the layer made of the molding material and the core metal plate can be reduced, and the electrical characteristics of the current collector plate can be improved.
- the oxide on the surface of the core metal plate is removed in advance, and a layer of a noble metal, a conductive inorganic oxide, a conductive inorganic nitride, or a conductive inorganic carbide is formed thereon. It can be formed as an electric good conductor layer.
- a current collector plate is formed by using a conductive material for forming a mixture of 80 wt% of graphite and 20 wt% of a phenol resin and surrounding a core metal plate.
- a mold was uniformly filled with 50 g of the molding compound, and pre-compressed at a mold clamping pressure of 100 kgf Z cm 2 . At this time, the mold temperature was 70.
- the mold is opened, a metal plate is inserted, 50 g of a molding compound is filled from above, the mold is tightened with a mold clamping pressure of 500 kgf cm 2 , and the temperature is reduced to 160 ° C. Up.
- the current-collecting plate manufactured in this way is stronger in strength and has lower electric resistance than the current-collecting plate (thickness: 7 mmm) made of only the conductive molding material. It has become possible to make it thinner.
- a 2 mm thick brass plate was used as the core material.
- the current collector plate was provided with a pair of manifold holes for oxidizing gas, fuel gas and coolant. The inner surfaces of the manifold holes are covered with a conductive molding material so that the core metal plate does not come into contact with the fluid flowing through each manifold hole.
- a stack using this current collector was prepared, and a power generation test was performed for 100 hours using pure water as a coolant. The number of stacked cells was 50 cells.
- the sputtering power was set to 400 W, and the deposition rate was set to 1.5 m / hour.
- a TiN layer was formed to a thickness of 1 Aim on the surface of a l-mm-thick Ti plate by a sputtering method using an RF-plana magnetron.
- TiN (99%) was used, and the substrate temperature was 500.
- Sputtering evening atmosphere and 4 X 1 0- 2 Torr of A r (9 9. 9 9 9 9%) was set to 4 0 0 W, the deposition speed becomes 1. 5 / xmZ Time .
- the obtained sputter layer was identified as TiN by structural analysis using X-ray diffraction.
- the specific resistance of T i N layer obtained by this method was filed with 2 X 1 0- 4 ⁇ cm.
- a Ti-Al-N layer having a thickness of 1.2 m was formed on the surface of an A1 plate having a thickness of 1 mm by a sputtering method using an RF-diode.
- T i — A 1 — N (99%) was used, and the substrate temperature was set at 300.
- Sputtering atmosphere is 4 X 1 0- 2 Torr of A r (9 9. 9 9 9 %), spatter power 3 0 0 W, the deposition rate was set to be 1. 0 m / time, this method
- the specific resistance of the Ti-A 1 -N layer obtained at 1 was 1 ⁇ 10 3 ⁇ cm.
- the deposition method used was a high-frequency glow discharge decomposition method at 14.56 MHz, and the gases to be decomposed were silane, methane (CH 4 ), diborane (PH 3 ) diluted with hydrogen, and P (S
- the film thickness of the ⁇ -doped SiC layer was adjusted to 100 A by controlling the film formation time.
- SiC layer A gold electrode was deposited thereon, and the specific resistance of the SiC layer was measured to be 50 ⁇ ⁇ cm.
- a Pb layer having a thickness of 1 / zm was formed on the surface of a stainless steel SUS316 plate having a thickness of l mm by vacuum heating evaporation. Deposition conditions at this time, 1 X 1 0- 7 Torr of A r (9 9. 9 9 9 9%) at ambient substrate temperature was 2 0 0. Next, a Pb layer was formed on the Pb-deposited surface of the Pb-deposited stainless steel plate by a sputtering method. The formation conditions are: oxygen partial pressure
- the sputtering power was controlled so that the atmosphere was 2 X 10 — 4 Torr in an Ar atmosphere (99.99.99%), the substrate temperature was 200 ° C, and the deposition rate was 3 ⁇ mZ. Resulting et a sputtering evening layers, the resistivity of the P B_ ⁇ layer obtained in P b O and identified t this way the structural analysis by X-ray diffraction was 5 X 1 0- 5 ⁇ cm .
- a layer of tin oxide doped with In was formed on the surface of stainless steel SUS316 with a thickness of l mm to a thickness of 0.5 m by vacuum electron beam evaporation. did.
- the degree of vacuum during deposition is A r gas atmosphere of 5 X 1 0- 6 Torr, the substrate temperature was set to 3 0 0.
- a current collector made of a carbon molding material in which a core metal plate that has been surface-treated as described above is embedded has improved electrical characteristics and less voltage loss than a current collector that uses an untreated metal plate. It was confirmed that.
- a current collector plate and an end plate for stack fastening are integrally formed.
- the thickness of this current collector plate was increased in the stacking direction to keep the electrical resistance extremely low.
- the current collector was made of a graphite plate, and its thickness was 70 mm.
- the electrical resistivity of this graphite plate was 1 mQ′cm in the plane direction and 1 ⁇ ⁇ ⁇ cm in the thickness direction. Since the plate thickness is 70 mm, the cell stack including the current collector plate is fastened by fastening members such as bolts, nuts, and springs. Fastened with a predetermined load.
- the current collector plate had a terminal at its end, to which a power extraction cable was connected.
- the detailed structure of the terminal is the same as that of the first embodiment.
- the present invention provides a low-cost, lightweight, and current-collecting plate that does not fear metal corrosion in the manifold hole.
- the electrode is humidified by the water generated by the reaction on the inlet side of the reaction gas supplied thereto.
- the durability of the electrode can be improved.
- it can be integrated with the separator located at the end, so that the number of parts can be reduced and the power generation loss due to the resistance component can be reduced. As a result, cost reduction and volume and weight efficiency of polymer electrolyte fuel cells can be achieved. Can be improved
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020037015116A KR100552174B1 (ko) | 2002-04-17 | 2003-04-14 | 고분자 전해질형 연료전지 |
JP2003585213A JPWO2003088395A1 (ja) | 2002-04-17 | 2003-04-14 | 高分子電解質型燃料電池 |
EP03746483A EP1422776A4 (en) | 2002-04-17 | 2003-04-14 | POLYMERIC ELECTROLYTE FUEL CELL |
US10/778,602 US7294423B2 (en) | 2002-04-17 | 2004-02-17 | Polymer electrolyte fuel cell having improved current collector plates and method of forming the same |
US11/866,954 US20080079186A1 (en) | 2002-04-17 | 2007-10-03 | Polymer electrolyte fuel cell having improved current collector plates and method of forming the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002114552 | 2002-04-17 | ||
JP2002-114552 | 2002-04-17 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/778,602 Continuation-In-Part US7294423B2 (en) | 2002-04-17 | 2004-02-17 | Polymer electrolyte fuel cell having improved current collector plates and method of forming the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003088395A1 true WO2003088395A1 (fr) | 2003-10-23 |
Family
ID=29243388
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/004723 WO2003088395A1 (fr) | 2002-04-17 | 2003-04-14 | Pile a combustible a electrolyte polymerique |
Country Status (6)
Country | Link |
---|---|
US (2) | US7294423B2 (ja) |
EP (1) | EP1422776A4 (ja) |
JP (1) | JPWO2003088395A1 (ja) |
KR (1) | KR100552174B1 (ja) |
CN (1) | CN1312796C (ja) |
WO (1) | WO2003088395A1 (ja) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1469542A1 (en) * | 2003-04-09 | 2004-10-20 | Matsushita Electric Industrial Co., Ltd. | Polymer electrolyte fuel cell |
JP2004362943A (ja) * | 2003-06-05 | 2004-12-24 | Fuji Electric Holdings Co Ltd | 燃料電池 |
JP2005285399A (ja) * | 2004-03-29 | 2005-10-13 | Toyota Motor Corp | 燃料電池 |
JP2005327558A (ja) * | 2004-05-13 | 2005-11-24 | Fuji Electric Holdings Co Ltd | 固体高分子形燃料電池 |
WO2006009277A1 (ja) * | 2004-07-22 | 2006-01-26 | Toyota Jidosha Kabushiki Kaisha | 集電板、燃料電池、及びそれらの製造方法 |
JP2006059679A (ja) * | 2004-08-20 | 2006-03-02 | Honda Motor Co Ltd | 燃料電池スタック |
JP2006080081A (ja) * | 2004-09-08 | 2006-03-23 | Samsung Sdi Co Ltd | 燃料電池システム及びスタック |
JP2006179300A (ja) * | 2004-12-22 | 2006-07-06 | Denso Corp | 燃料電池の電流測定装置に用いられる電流量推定システム |
JP2006185671A (ja) * | 2004-12-27 | 2006-07-13 | Denso Corp | 燃料電池の電流測定装置 |
JP2007059127A (ja) * | 2005-08-23 | 2007-03-08 | Honda Motor Co Ltd | 燃料電池及び燃料電池を搭載した自動二輪車 |
JP2007250189A (ja) | 2006-02-20 | 2007-09-27 | Nissan Motor Co Ltd | 燃料電池スタック |
JP2008177047A (ja) * | 2007-01-18 | 2008-07-31 | Mitsubishi Materials Corp | 燃料電池 |
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US7722977B2 (en) | 2004-08-20 | 2010-05-25 | Honda Motor Co., Ltd. | Fuel cell stack comprising current collector provided at least at one fluid passage |
JP2010282944A (ja) * | 2009-06-04 | 2010-12-16 | Chung-Hsin Electric & Machinery Manufacturing Corp | 透明な流路を具えた燃料電池スタック及びそのバイポーラ板構造 |
WO2013073330A1 (ja) | 2011-11-14 | 2013-05-23 | 日本軽金属株式会社 | 燃料電池用集電板及びその製造方法 |
JP2013125611A (ja) * | 2011-12-13 | 2013-06-24 | Panasonic Corp | 燃料電池用セパレータ、及び燃料電池 |
JP2018147716A (ja) * | 2017-03-06 | 2018-09-20 | トヨタ自動車株式会社 | 燃料電池用のターミナルプレート |
JP2021022476A (ja) * | 2019-07-26 | 2021-02-18 | 京セラ株式会社 | セルスタック装置、燃料電池モジュールおよび燃料電池装置 |
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DE102006049031B4 (de) * | 2006-10-13 | 2009-10-22 | Futuree Fuel Cell Solutions Gmbh | Tragbehälter einer Energieversorgungseinheit mit Brennstoffzellen, dessen Verwendung und Verfahren zur Gefährdungsreduzierung |
US20080206605A1 (en) * | 2007-02-28 | 2008-08-28 | Bloom Energy Corporation | Current collector for fuel cell systems |
FR2971092B1 (fr) * | 2011-02-02 | 2013-03-08 | Peugeot Citroen Automobiles Sa | Pile a combustible comportant une plaque monopolaire collectrice |
US9076997B2 (en) | 2011-06-23 | 2015-07-07 | Nippon Mektron, Ltd | Flexible circuit board and method for manufacturing the same, and fuel cell using the flexible circuit board |
WO2013114811A1 (ja) * | 2012-01-30 | 2013-08-08 | 日本特殊陶業株式会社 | 燃料電池 |
US10044054B2 (en) * | 2014-03-28 | 2018-08-07 | Nissan Motor Co., Ltd. | Laminated battery, separator and connection method of internal resistance measuring device |
EP3035430B1 (de) * | 2014-12-19 | 2019-09-25 | Hexis AG | Brennstoffzellenmodul |
JP6392688B2 (ja) * | 2015-03-09 | 2018-09-19 | 日本特殊陶業株式会社 | 燃料電池スタック |
JP7152202B2 (ja) * | 2018-06-28 | 2022-10-12 | トヨタ自動車株式会社 | 燃料電池用セパレータ及び燃料電池 |
JP7347197B2 (ja) * | 2019-12-19 | 2023-09-20 | トヨタ自動車株式会社 | 回転電機コアの製造方法および製造装置 |
DE102022212229A1 (de) | 2022-11-17 | 2024-05-23 | Robert Bosch Gesellschaft mit beschränkter Haftung | Verfahren zum Herstellen eines Brennstoffzellenstapels, Brennstoffzellenstapel sowie Vorrichtung |
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Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7678490B2 (en) | 2003-04-09 | 2010-03-16 | Panasonic Corporation | Polymer electrolyte fuel cell |
EP1469542A1 (en) * | 2003-04-09 | 2004-10-20 | Matsushita Electric Industrial Co., Ltd. | Polymer electrolyte fuel cell |
JP2004362943A (ja) * | 2003-06-05 | 2004-12-24 | Fuji Electric Holdings Co Ltd | 燃料電池 |
JP2005285399A (ja) * | 2004-03-29 | 2005-10-13 | Toyota Motor Corp | 燃料電池 |
JP2005327558A (ja) * | 2004-05-13 | 2005-11-24 | Fuji Electric Holdings Co Ltd | 固体高分子形燃料電池 |
JP4609732B2 (ja) * | 2004-07-22 | 2011-01-12 | トヨタ自動車株式会社 | 集電板、燃料電池、及びそれらの製造方法 |
US7947408B2 (en) | 2004-07-22 | 2011-05-24 | Toyota Jidosha Kabushiki Kaisha | Collecting plate, fuel cell, and method for manufacturing same |
JPWO2006009277A1 (ja) * | 2004-07-22 | 2008-07-31 | トヨタ自動車株式会社 | 集電板、燃料電池、及びそれらの製造方法 |
WO2006009277A1 (ja) * | 2004-07-22 | 2006-01-26 | Toyota Jidosha Kabushiki Kaisha | 集電板、燃料電池、及びそれらの製造方法 |
US7722977B2 (en) | 2004-08-20 | 2010-05-25 | Honda Motor Co., Ltd. | Fuel cell stack comprising current collector provided at least at one fluid passage |
JP2006059679A (ja) * | 2004-08-20 | 2006-03-02 | Honda Motor Co Ltd | 燃料電池スタック |
JP2006080081A (ja) * | 2004-09-08 | 2006-03-23 | Samsung Sdi Co Ltd | 燃料電池システム及びスタック |
JP4672492B2 (ja) * | 2004-09-08 | 2011-04-20 | 三星エスディアイ株式会社 | 燃料電池システム及びスタック |
JP2006179300A (ja) * | 2004-12-22 | 2006-07-06 | Denso Corp | 燃料電池の電流測定装置に用いられる電流量推定システム |
JP2006185671A (ja) * | 2004-12-27 | 2006-07-13 | Denso Corp | 燃料電池の電流測定装置 |
JP2007059127A (ja) * | 2005-08-23 | 2007-03-08 | Honda Motor Co Ltd | 燃料電池及び燃料電池を搭載した自動二輪車 |
JP2007250189A (ja) | 2006-02-20 | 2007-09-27 | Nissan Motor Co Ltd | 燃料電池スタック |
JP2008177047A (ja) * | 2007-01-18 | 2008-07-31 | Mitsubishi Materials Corp | 燃料電池 |
JP2009117208A (ja) * | 2007-11-07 | 2009-05-28 | Ngk Spark Plug Co Ltd | 固体酸化物形燃料電池 |
JP2009140794A (ja) * | 2007-12-07 | 2009-06-25 | Toyota Motor Corp | 燃料電池用のターミナルプレートと燃料電池 |
JP2010282944A (ja) * | 2009-06-04 | 2010-12-16 | Chung-Hsin Electric & Machinery Manufacturing Corp | 透明な流路を具えた燃料電池スタック及びそのバイポーラ板構造 |
WO2013073330A1 (ja) | 2011-11-14 | 2013-05-23 | 日本軽金属株式会社 | 燃料電池用集電板及びその製造方法 |
JP2013125611A (ja) * | 2011-12-13 | 2013-06-24 | Panasonic Corp | 燃料電池用セパレータ、及び燃料電池 |
JP2018147716A (ja) * | 2017-03-06 | 2018-09-20 | トヨタ自動車株式会社 | 燃料電池用のターミナルプレート |
JP2021022476A (ja) * | 2019-07-26 | 2021-02-18 | 京セラ株式会社 | セルスタック装置、燃料電池モジュールおよび燃料電池装置 |
Also Published As
Publication number | Publication date |
---|---|
CN1516904A (zh) | 2004-07-28 |
US20080079186A1 (en) | 2008-04-03 |
KR20030097887A (ko) | 2003-12-31 |
CN1312796C (zh) | 2007-04-25 |
EP1422776A1 (en) | 2004-05-26 |
EP1422776A4 (en) | 2008-02-20 |
US7294423B2 (en) | 2007-11-13 |
US20040209151A1 (en) | 2004-10-21 |
JPWO2003088395A1 (ja) | 2005-08-25 |
KR100552174B1 (ko) | 2006-02-13 |
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