WO2015049859A1 - 燃料電池用セパレーターおよび燃料電池 - Google Patents
燃料電池用セパレーターおよび燃料電池 Download PDFInfo
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- WO2015049859A1 WO2015049859A1 PCT/JP2014/004991 JP2014004991W WO2015049859A1 WO 2015049859 A1 WO2015049859 A1 WO 2015049859A1 JP 2014004991 W JP2014004991 W JP 2014004991W WO 2015049859 A1 WO2015049859 A1 WO 2015049859A1
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- Prior art keywords
- separator
- groove
- fuel cell
- surface side
- central region
- Prior art date
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- 239000000446 fuel Substances 0.000 title claims description 88
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims description 51
- 238000010248 power generation Methods 0.000 claims description 39
- 230000000630 rising effect Effects 0.000 claims description 39
- 238000001816 cooling Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract 1
- 239000002737 fuel gas Substances 0.000 description 57
- 239000007789 gas Substances 0.000 description 57
- 239000000498 cooling water Substances 0.000 description 44
- 239000007800 oxidant agent Substances 0.000 description 23
- 230000001590 oxidative effect Effects 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 10
- 230000002093 peripheral effect Effects 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Images
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
- H01M8/02—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
- H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
-
- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
-
- 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
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
- H01M8/248—Means for compression of the fuel cell stacks
-
- 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
- H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Definitions
- the present invention relates to a fuel cell separator and a fuel cell.
- the fuel cell has a stack structure in which a plurality of fuel cells serving as a power generation unit are stacked, and each fuel cell sandwiches a membrane electrode assembly between opposing separators.
- a method of forming a concave groove serving as a gas flow path for fuel gas and a concave groove serving as a cooling water flow path on the front and back surfaces of a separator by forming a plurality of concave and convex stripes by press molding is disclosed in, for example, This is proposed in Japanese Patent No. -54872.
- the structure can be simplified, the fuel cell stacking direction can be shortened, and a large number of fuel cells can be stacked.
- the fuel cell is mounted on, for example, a vehicle or the like in a state in which the stacked fuel cells are fastened by applying a force in the stacking direction, and the fastening force is constantly applied to each fuel cell. Since the fastening force to each part of the cell, such as the power generation region of the fuel cell and its surroundings, is not always uniform, the following problems may occur when the fastening force is always applied.
- the outer edge of the separator for the fuel cell extends outward from the central region of the separator facing the power generation region of the membrane electrode assembly.
- the outer edge of the separator for the fuel cell is connected to the periphery of the membrane electrode assembly and this.
- the sealing member to seal will overlap.
- the outer peripheral portion of the fuel cell separator tends to increase the thickness of the peripheral edge of the membrane electrode assembly that is to be sandwiched between other separators.
- the opposing region is a power generation region of the membrane electrode assembly, no other member such as a seal member is interposed, so that the membrane electrode junction that is to be sandwiched between other separators Body thickness is almost uniform.
- the present invention can be implemented as the following modes.
- the 1st aspect provides the separator for fuel cells which has the 2nd surface which makes the back surface of the 1st surface and 1st surface assembled
- the fuel cell separator according to the first aspect includes a central region facing the power generation possible region of the membrane electrode assembly, a flat outer edge extending from the central region to an outer edge, and the first surface, A first surface-side groove formed in the central region; and a second surface-side groove formed in the central region on the second surface.
- the groove of the first surface side concave groove portion and the groove of the second surface side concave groove portion are formed by forming a plurality of concave and convex stripes by press molding on the central region, and the first surface and the second groove in the central region.
- the bottom wall of the first surface side groove portion at the boundary position where the end portion of another member different from the membrane electrode assembly can be located in the first surface side groove portion is arranged alternately on the surface, The rising height from the groove opening end is lower than the bottom wall of the other first surface side groove.
- the separator for a fuel cell according to the first aspect is the rising height of the bottom wall from the groove opening end of the first surface side groove at the boundary position where the edge of another member different from the membrane electrode assembly can be located. Is configured to be lower than the bottom wall of the other first surface side groove portion located in the central region of the separator. Therefore, when the surface pressure is applied to the central region of the separator and the flat outer edge extending to the outer edge of the separator, the bottom wall rises from the groove opening end according to the fuel cell separator according to the first aspect. Since the height is low, the surface pressure applied to the periphery of the first surface side groove portion at the boundary position can be relaxed from the periphery of the other first surface side groove portion positioned on the separator central region side.
- the surface pressure is applied to the central region of the separator and the flat outer edge extending to the outer edge of the separator while sandwiching the membrane electrode assembly with the other separator. Even if it is applied, buckling of the membrane electrode assembly and damage to the electrolyte membrane can be avoided or suppressed by reducing the surface pressure around the first surface side groove at the boundary position.
- the boundary position is located on the outer edge side of the first surface side groove portion, and the first surface side recess on the outer edge portion side of the first surface side groove portion.
- the rising height of the bottom wall of the groove may be lower than the bottom wall of the other first surface side concave groove. Further, the rising height of the bottom wall of the first surface side groove portion located closest to the outer edge portion among the bottom grooves of the first surface side groove portion on the outer edge side of the first surface side groove portion. However, you may be lower than the said bottom part wall of the said other said 1st surface side recessed groove part located in the said center area
- the rising height of the bottom wall of the one or more outer edge portions or the first surface side concave groove portion on the outermost edge side may be reduced.
- the discharge height By adjusting the discharge height, the rising height can be easily reduced. Therefore, according to the fuel cell separator according to the first aspect, it is possible to reduce the manufacturing cost, and it is possible to eliminate or suppress problems that may occur due to the fastening force reaching by simple measures such as mold adjustment.
- the second aspect provides a fuel cell separator having a first surface and a second surface forming the back surface of the first surface, which are assembled to the membrane electrode assembly.
- the fuel cell separator according to the second aspect extends from the central region corresponding to the power generation possible region of the membrane electrode assembly to the outer edge from the separator central region facing the power generation region of the membrane electrode assembly.
- a flat outer edge portion in the separator central region in the first surface, in a first surface-side groove formed on one surface side, in the separator central region in the second surface And a second surface side groove portion formed on the other surface side, and the groove of the first surface side groove portion and the groove of the second surface side groove portion are press-molded with respect to the central region of the separator.
- the first surface and the second surface are alternately arranged on the front and back surfaces of the separator in the central region of the separator, and the outermost edge side of the first surface side concave groove portion
- the bottom wall of the first surface side groove portion located on the outermost edge side to be placed is more than the bottom wall of the other first surface side groove portion located in the central region located in the central region of the separator, The rising height from the opening end of the groove is low.
- the rising height of the bottom wall from the groove opening end of the first surface-side groove located on the outermost edge side located on the outermost edge side is the second aspect. Is configured so as to be lower than the bottom wall of the other first surface side groove portion located in the central region of the separator. Therefore, when the surface pressure is applied to the central region of the separator and the flat outer edge extending to the outer edge of the separator, according to the fuel cell separator according to the first aspect, the bottom from the groove opening end Since the rising height of the wall is low, the surface pressure applied to the periphery of the first surface side groove portion extending on the outer edge portion extending on the outer edge portion side is increased on the separator central region side.
- the separator and the membrane electrode assembly are sandwiched between the separator central region and the flat outer edge extending to the outer edge of the separator. Even when surface pressure is applied, buckling of the membrane electrode assembly and avoiding damage to the electrolyte membrane are achieved by reducing the surface pressure around the first groove groove extending on the outermost edge side on the outermost edge side. Or, suppression becomes possible.
- the rising height of the bottom wall of the first surface-side groove extending most on the outer edge portion may be reduced, and the discharge height of the press die may be reduced.
- the fuel cell separator of the above aspect according to the second aspect it is possible to reduce the manufacturing cost, and to solve the problem that may occur due to the fastening force reaching by simple measures such as mold adjustment or Can be suppressed.
- a fuel cell according to a third aspect is a fuel cell in which a plurality of fuel cells each sandwiching a membrane electrode assembly between a first separator and a second separator are stacked, each of the fuel cells being a first cell
- any one of the fuel cell separators according to the second aspect is provided as the first separator, and the outer edge portion is joined to the outside of the power generation region of the membrane electrode assembly.
- the bottom wall of the first surface side groove portion included in the first separator of one of the fuel cells is the second wall of the other fuel cell. It is in contact with the separator.
- the first separator sandwiching the membrane electrode assembly is provided with the first surface side concave groove extending on the side of the flat outer edge extending from the separator central region to the outer edge.
- a separator that can relieve the surface pressure around the groove on the surface side.
- the separator central region of the first separator is opposed to the power generation region of the membrane electrode assembly, and the outer edge portion of the first separator is attached to the membrane. Join the electrode assembly outside the power generation area.
- the surface pressure applied from the central region of the separator to the outer edge portion on the outer side is around the first surface side groove portion extending on the outer edge portion side where the seal portion is interposed. Is alleviated.
- the buckling of the membrane electrode assembly and the damage to the electrolyte membrane can be avoided or suppressed, and the battery life can be extended and the battery performance can be maintained.
- the first separator in which the rising height of the bottom wall of the first surface side groove portion extending on the outer edge side is lowered can be replaced with the existing fuel cell.
- the first surface side groove portion in the separator central region of the first separator can be a flow path for the gas supplied to the membrane electrode assembly.
- the bottom wall of the first surface side concave groove portion of the first separator of one fuel cell stacked adjacent to each other is brought into contact with the second separator of another fuel cell, so that the second surface side concave portion is brought into contact.
- the groove portion is closed, and the closed second surface side groove portion can be used as a cooling water flow path through which the cooling water passes.
- the present invention can be realized in various forms, for example, in the form of a fuel cell manufacturing method or a fuel battery cell.
- FIG. 2 is a schematic perspective view showing an exploded configuration of a unit cell 100.
- 3 is a schematic plan view showing a configuration of an anode separator 120.
- FIG. 4 is a schematic perspective view showing an enlarged part of a fuel gas flow channel groove 202 along the Y direction in the fuel gas flow channel 200 in the conversion region A shown in FIG. 3.
- FIG. 5 is a schematic cross-sectional view of the fuel cell 10 taken along line 5-5 at an enlarged portion of part C in FIG.
- FIG. 5 is an explanatory diagram showing the relationship between the rising height when the unit cell 100 of the present embodiment is viewed in a cross-section along line 5-5 in the enlarged portion of C part in FIG. 3.
- FIG. 1 is a schematic perspective view showing the configuration of a fuel cell 10 as an embodiment of the present invention.
- the fuel cell 10 has a stack structure in which a plurality of unit cells 100 as fuel cells are stacked in the Z direction (hereinafter also referred to as “stacking direction”) and sandwiched between a pair of end plates 170F and 170E.
- the fuel cell 10 has a front end side terminal plate 160F between a front end side end plate 170F and the unit cell 100 with a front end side insulating plate 165F interposed therebetween.
- the fuel cell 10 has a rear end side terminal plate 160E between the rear end side end plate 170E and the unit cell 100 with a rear end side insulating plate 165E interposed therebetween.
- the unit cell 100, the terminal plates 160F and 160E, the insulating plates 165F and 165E, and the end plates 170F and 170E each have a plate structure having a substantially rectangular outer shape, and the long sides are in the X direction (horizontal direction). ) And the short sides are arranged along the Y direction (vertical direction, vertical direction).
- the end plate 170F, the insulating plate 165F, and the terminal plate 160F on the front end side include a fuel gas supply hole 172IN and a fuel gas discharge hole 172OT, a plurality of oxidant gas supply holes 174IN and an oxidant gas discharge hole 174OT, and a plurality of cooling waters. It has a supply hole 176IN and a cooling water discharge hole 176OT. These supply / discharge holes are connected to respective holes (not shown) provided at corresponding positions of the unit cells 100 to constitute gas / cooling water supply / discharge manifolds corresponding to the respective holes.
- these supply / discharge holes are not provided in the end plate 170E, the insulating plate 165E, and the terminal plate 160E on the rear end side. This is because the reaction gas (fuel gas, oxidant gas) and cooling water are supplied from the front end plate 170F to each unit cell 100 via the supply manifold, while the exhaust gas from each unit cell 100 is discharged.
- the fuel cell is a type that discharges discharged water from the front end side end plate 170F to the outside through a discharge manifold.
- the present invention is not limited to this, for example, a type in which reaction gas and cooling water are supplied from the end plate 170F on the front end side, and exhaust gas and discharge water are discharged to the outside from the end plate 170E on the rear end side.
- the plurality of oxidant gas supply holes 174IN are arranged along the X direction (long side direction) at the outer edge of the lower end of the front end side end plate 170F, and the plurality of oxidant gas discharge holes 174OT are arranged at the outer edge of the upper end. It is arrange
- the fuel gas supply hole 172IN is disposed at the upper end in the Y direction (short side direction) of the outer edge at the right end of the front end plate 170F, and the fuel gas discharge hole 172OT is disposed in the Y direction at the outer edge at the left end. It is arranged at the lower end.
- the plurality of cooling water supply holes 176IN are arranged along the Y direction below the oxidant gas supply holes 174IN, and the plurality of cooling water discharge holes 176OT are arranged above the oxidant gas discharge holes 174OT in the Y direction. Are arranged along.
- the front end side terminal plate 160F and the rear end side terminal plate 160E are power collecting plates for the generated power of each unit cell 100, and output the power collected from terminals not shown to the outside.
- FIG. 2 is a schematic perspective view showing the structure of the unit cell 100 in an exploded manner.
- the unit cell 100 includes a membrane electrode gas diffusion layer assembly (MEGA) 110, a gas diffusion layer assembly 110, an anode separator 120 disposed so as to sandwich both sides of the MEGA 110, and a cathode separator. 130, an adhesive seal 140, and a gas flow path member 150.
- MEGA membrane electrode gas diffusion layer assembly
- the MEGA 110 includes a membrane electrode assembly (MEA: Membrane Electrode Assembly) in which a pair of catalyst electrode layers are formed on both surfaces of an electrolyte membrane, and the MEA is a gas diffusion layer (Gas Diffusion Layer / GDL) that allows gas diffusion through the MEA. It is a power generator configured to be sandwiched. Note that MEGA may be referred to as MEA.
- MEA Membrane Electrode Assembly
- the anode-side separator 120 and the cathode-side separator 130 are composed of members having gas barrier properties and electronic conductivity, for example, carbon members such as dense carbon that compresses carbon particles and makes gas impermeate, It is made of a press-molded metal member such as stainless steel or titanium steel. In this embodiment, the anode-side separator 120 was produced by press molding stainless steel.
- the anode-side separator 120 includes a plurality of groove-shaped fuel gas flow paths on the MEGA 110 side surface, and a plurality of groove-shaped cooling water flow paths on the opposite surface. They are arranged alternately on the back side. These flow paths will be described later.
- the anode-side separator 120 includes a fuel gas supply hole 122IN and a fuel gas discharge hole 122OT, a plurality of oxidant gas supply holes 124IN and an oxidant gas discharge hole 124OT, and a plurality of supply and discharge holes constituting the manifold described above.
- a cooling water supply hole 126IN and a cooling water discharge hole 126OT are provided.
- the cathode separator 130 includes a fuel gas supply hole 132IN and a fuel gas discharge hole 132OT, a plurality of oxidant gas supply holes 134IN and an oxidant gas discharge hole 134OT, a plurality of cooling water supply holes 136IN and a cooling water discharge. Hole 136OT.
- the fuel gas supply hole 142IN and the fuel gas discharge hole 142OT, and the plurality of oxidant gas supply holes 144IN and the oxidant corresponding to the supply / discharge holes of the anode separator 120 are provided in the adhesive seal 140.
- a gas discharge hole 144OT, a plurality of cooling water supply holes 146IN, and a cooling water discharge hole 146OT are provided.
- the adhesive seal 140 is formed of a resin or rubber having sealing properties and insulating properties, and has a power generation region window 141 adapted to the rectangular shape of the MEGA 110 at the center thereof.
- the peripheral edge of the power generation area window 141 has a stepped shape, and the MEGA 110 is assembled and attached to the stepped portion.
- the MEGA 110 thus mounted on the power generation region window 141 is overlapped with the adhesive seal 140 at the step portion of the adhesive seal 140, and the region exposed at the power generation region window 141 is supplied with fuel gas from the anode-side separator 120 described later.
- It is defined as a power generation possible region 112 (hereinafter referred to as “power generation region”) capable of generating power by an electrochemical reaction at least in part.
- the adhesive seal 140 includes the supply / discharge holes described above in the peripheral region of the power generation region window 141 in which the MEGA 110 is incorporated, and the anode-side separator 120 and the cathode-side separator 130 are connected in a state where the MEGA 110 is incorporated in the power generation region window 141. , Seal around each supply and discharge hole. That is, the adhesive seal 140 seals the MEGA 110 at the step portion over the outer region of the power generation region 112 and also seals the rectangular outer peripheral surface of the MEGA 110 between the anode side separator 120 and the cathode side separator 130. .
- a fuel gas sealing material 300, an oxidant sealing material 301, and a cooling water sealing material 302 are provided.
- the gas flow path member 150 is located between the MEGA 110 and the cathode side separator 130 with the adhesive seal 140 interposed therebetween, and the oxidant gas supplied from the oxidant gas supply hole 134IN of the cathode side separator 130 is A gas flow path for flowing along the surface direction (XY plane direction) of the MEGA 110 to discharge from the oxidant gas discharge hole 134OT is formed.
- a porous material having gas diffusibility and conductivity such as a metal porous body (for example, expanded metal) is used.
- the gas flow path member 150 includes gas-impermeable thin leaf-like sealing sheets 151 at the upper and lower ends in FIG. 2, and the sheets are joined to the upper and lower end regions of the MEGA 110.
- the cathode-side separator 130 has a substantially flat plate shape including the above-described supply / exhaust hole formation region, and the legs 131 protrude in the vicinity of the upper and lower ends of the gas flow path member 150 in FIG. I am letting.
- the legs 131 come into contact with an outer edge portion 123 (described later) in the anode-side separator 120 of the adjacent unit cell 100. This situation will be described later.
- FIG. 3 is a schematic plan view showing the configuration of the anode separator 120.
- FIG. 3 shows a state as viewed from the surface facing the other unit cell 100 adjacent to the anode separator 120 (hereinafter also referred to as “cooling surface”).
- a surface facing the MEGA 110 opposite to the cooling surface is also referred to as a “gas surface”.
- the anode-side separator 120 is formed by press-molding stainless steel or the like, and sandwiches the MEGA 110 together with the cathode-side separator 130 with an adhesive seal 140 and a gas flow path member 150 interposed therebetween as shown in FIG.
- This anode-side separator 120 is provided with a plurality of first grooves 202 and second grooves 204, which will be described later, alternately arranged in the separator central area 121 facing the power generation area 112 described above of the MEGA 110, and outside the separator central area 121.
- the outer peripheral edge portion 123 extending to the center region and surrounding the central region has a fuel gas supply hole 122IN, a fuel gas discharge hole 122OT, and a plurality of oxidant gas supply holes as the reaction gas and cooling water supply / discharge holes described above. 124IN and oxidant gas discharge hole 124OT, and a plurality of cooling water supply holes 126IN and cooling water discharge holes 126OT.
- the fuel gas supply hole 122IN and the fuel gas discharge hole 122OT are individually sealed by the fuel gas sealing material 300, and have a plurality of oxidant gas supply holes 124IN and a plurality of oxidant gas discharge holes 124OT. Is sealed for each row of holes by the oxidant sealing material 301. Further, the plurality of cooling water supply holes 126IN and the cooling water discharge holes 126OT are sealed by the cooling water sealing material 302 including the separator central region 121 on the cooling surface side.
- the first groove 202 is a concave groove on the gas surface side (first surface) of the anode separator 120 described above, and is concave on the back surface side in FIG. 3, and extends in this gas surface.
- the second groove 204 is a concave groove that is concave on the cooling surface side (second surface) of the anode-side separator 120 described above, and in FIG. Then, the first groove 202 and the second groove 204 are formed as a plurality of concave and convex strips by press molding that presses a concave and convex mold adapted to both groove shapes against the separator central region 121, and in the separator central region 121.
- the anode-side separator 120 is alternately arranged on the front and back surfaces (first surface and second surface). That is, the anode-side separator 120 has a cross-sectional uneven shape (cross-sectional corrugated shape) in which the first grooves 202 and the second grooves 204 are alternately and repeatedly arranged in a longitudinal sectional view in FIG.
- the first groove 202 that is concave on the gas surface side is a fuel gas passage groove that supplies fuel gas to the MEGA 110 exposed to the power generation area window 141 of the adhesive seal 140 (hereinafter also referred to as “fuel gas passage groove 202”).
- fuel gas passage groove 202 constitutes the 1st surface side recessed groove part.
- the second groove 204 that is concave on the cooling surface side constitutes a rib that partitions the fuel gas flow channel groove 202, and the cooling water flow through which the cooling water passes when the anode separator 120 comes into contact with the cathode separator 130 described later.
- a channel groove (hereinafter also referred to as “cooling water channel groove 204”) is formed.
- the plurality of second grooves 204 constitutes a second surface side recessed groove portion, and the fuel gas flow path 200 formed of the plurality of fuel gas flow path grooves 202 is connected to the fuel gas discharge hole from the fuel gas supply hole 122IN. It is formed in a serpentine shape toward 122OT on the gas surface side described above on the back side of the paper in FIG.
- the unit cell 100 of the present embodiment includes a serpentine-shaped fuel gas flow channel 200 in which a fuel gas flow channel groove 202 positioned on the upper and lower ends of the separator central region 121 shown in FIG.
- the region 121 extends in the left-right direction, that is, the x direction in FIG.
- the separator central region 121 faces the power generation region 112 of the MEGA 110, the fuel gas flow path extending in the left-right direction of the separator central region 121 on the outer edge 123 side also on the periphery of the power generation region 112 Fuel gas can be supplied from the groove 202. 3, the first groove 202 that is positioned on the upper and lower ends of the separator central region 121 and extends in the left-right direction of the separator central region 121 on the outer edge portion 123 side is provided in the separator central region. In order to distinguish from the 1st groove
- the first groove 202 functions as a rib that partitions the cooling water flow channel groove 204 on the cooling surface side in the linear flow channel region extending in the X direction, including the conversion region A.
- the fuel gas channel groove 202 functions as a rib that partitions the coolant channel groove 204 in the linear channel region extending in the X direction, the flow of the coolant in the second groove 204 toward the coolant discharge hole 126OT side. Does not disturb.
- the fuel gas flow channel groove 202 serves as a wall, and the flow of the cooling water from the cooling water supply hole 126IN to the cooling water discharge hole 126OT can be hindered. Therefore, this is prevented by adopting the structure described below for the fuel gas passage groove 202 in this region.
- FIG. 4 is a schematic perspective view showing a part of the fuel gas channel groove 202 along the Y direction in the fuel gas channel 200 in the conversion region A shown in FIG. 3 in an enlarged manner.
- the upper side is the cooling surface side
- the lower side is the gas surface side.
- a shallow groove 208 is formed in the fuel gas passage groove 202 formed along the Y direction.
- the shallow groove portion 208 is a portion having a shallower depth than other portions (hereinafter also referred to as “deep groove portion 206”).
- the depth of the fuel gas flow channel 202 means the distance from the position of the portion of the gas surface of the anode separator 120 in contact with the MEGA 110 to the bottom of the fuel gas flow channel 202.
- the depth of the fuel gas flow channel groove 202 is deep at the position of the deep groove portion 206 and becomes shallow at the position of the shallow groove portion 208, the deep groove portion 206 and the shallow groove portion 208 are different in the fuel gas flow in the conversion region A of FIG. Although they are alternately arranged along the groove path of the road groove 202, none of them is in contact with the MEGA 110. Therefore, the fuel gas channel groove 202 allows the fuel gas to pass along the Y direction in FIG. 4 and along the channel groove path in the conversion region A in FIG. In this case, the depth of the deep groove 206 is the same as that of the fuel gas flow channel 202 in the flow channel other than the conversion region A.
- the anode separator 120 is formed on the surface of the cathode separator 130 of the adjacent unit cell 100 on the bottom wall of each deep groove 206.
- the outer peripheral surface of 202 s, the ceiling surface in the illustration of FIG. 4, is brought into contact, and the cathode-side separator 130 is not contacted at the position of the shallow groove portion 208.
- communication is established between the surface of the cathode side separator 130 and the two adjacent cooling water passage grooves 204 with the shallow groove portion 208 interposed therebetween.
- a channel groove 205 is formed.
- the cooling water can flow not only in the Y direction along the cooling water channel groove 204 but also in the X direction via the communication channel groove 205.
- the flow of the cooling water flowing through the cooling water flow channel 204 along the X direction can be prevented from being blocked by the fuel gas flow channel 202 along the Y direction.
- the reverse case the same applies to the reverse case.
- the shallow groove portion 208 is also formed in the fuel gas passage groove 202 along the X direction of the conversion area A shown in FIG. Thereby, it is possible to prevent the flow of the cooling water flowing through the cooling water passage groove 204 parallel to the fuel gas passage groove 202 along the Y direction from being blocked by the fuel gas passage groove 202 along the X direction. it can. Therefore, the anode-side separator 120 does not block the cooling water supplied from the cooling water supply hole 126IN by the fuel gas passage groove 202 along either the X direction or the Y direction. It is possible to flow toward 126 OT.
- the anode-side separator 120 is provided with the fuel gas flow channel grooves 202 alternately arranged in the deep groove portions 206 and the shallow groove portions 208 along the groove paths in the conversion region A of FIG.
- the anode-side separator 120 has a linear path in the serpentine-shaped groove path, that is, in the x direction in FIG. 3, other fuel gas flow path grooves 202 including the gas surface side end first grooves 202t, and cooling water
- the cooling water passage groove 204 on the side has a simple concave groove shape.
- FIG. 5 is a schematic cross-sectional view of the fuel cell 10 taken along line 5-5 at the enlarged portion C in FIG.
- the fuel cell 10 is configured by stacking a plurality of unit cells 100, and the unit cell 100 sandwiches the MEGA 110 between an anode-side separator 120 and a cathode-side separator 130.
- the MEGA 110 is shown in a form in which an MEA 110D having a catalyst electrode layer bonded to both membrane surfaces of the electrolyte membrane is sandwiched between the anode-side gas diffusion layer 110A and the cathode-side gas diffusion layer 110C.
- Each unit cell 100 includes an outer edge portion 123 (see FIGS.
- each unit cell 100 is brought into contact with the separator central region 121 in which the first groove 202 and the second groove 204 are formed facing the power generation region 112 of the MEGA 110.
- the end first groove 202t and the first groove 202 in another part function as the fuel gas flow channel 202 extending as described above, with the concave groove opening end closed by the MEGA 110.
- the unit cells 100 stacked adjacent to each other include the bottom wall 202s of the first groove 202 and the end bottom wall 202ts of the end first groove 202t included in the anode separator 120 of one unit cell 100, and the other unit.
- the cathode side separator 130 of the cell 100 is brought into contact.
- the second groove 204 functions as the cooling water channel groove 204 that extends as described above, with the concave groove opening end closed.
- the legs 131 included in the cathode separator 130 of one unit cell 100 are brought into contact with the outer edge 123 of the anode separator 120 of the other unit cell 100.
- the legs 131 function as supports for the unit cells 100 at the outer edge portion 123 of the anode separator 120.
- the fuel cell 10 in which the unit cells 100 are stacked in this way is fastened in the cell stacking direction by a fastening shaft or the like (not shown), and the fastening force is generated by each part of each unit cell 100, specifically, the power generation of the MEGA 110. It always extends not only to the region 112 but also to the region of the outer edge 123.
- FIG. 6 is an explanatory diagram for explaining a situation in which an excessive surface pressure is assumed when the constituent members of the unit cell 100 are within the standard dimensions or when the assembly accuracy is within an allowable range.
- FIG. 6A shows a situation in which the assembly accuracy of the MEGA 110, the adhesive seal 140, and the gas flow path member 150 is secured.
- the thickness may increase at the outer edge 123 at the periphery of the MEGA 110 that is the object to be clamped with the cathode separator 130, specifically, at the periphery of the power generation region 112 shown in FIG. That is, the thickness in the stacking direction is the power generation region 112 at the boundary position where the end of the sealing sheet 151 of the gas flow path member 150 and the adhesive seal 140 which is another member different from the MEGA 110 are stacked. It may be thicker than the thickness in the stacking direction.
- the thickness of the MEGA 110 that is the object to be sandwiched between the cathode side separator 130 is substantially uniform.
- FIG. 7 is an explanatory diagram for explaining the technical idea conventionally employed in forming the anode-side separator
- FIG. 8 is an explanatory diagram for explaining the technical idea adopted in this embodiment.
- the end first groove 202t and the first groove 202 are both included in the separator central region 121 (see FIGS. 2 and 3).
- the anode-side separator 120H of this comparative example treats the end first groove 202t extending on the outer edge portion 123 side and the other first groove 202 located inside the separator central region 121 in an equivalent manner.
- the rising height from the opening end to the end bottom wall 202ts of the end first groove 202t (hereinafter referred to as the end side rising height Ht), and from the recessed groove opening end to the bottom wall 202s of the other first groove 202
- the end-side rising height Ht of the end first groove 202 t is the rising height Hs of the other first groove 202.
- the difference ⁇ H becomes a negative value so as to be lower, and the difference ⁇ H is set to ⁇ 0.01 to ⁇ 0.03. That is, even if the actual dimensions of the end side rising height Ht of the end first groove 202t and the rising height Hs of the other first groove 202 are within manufacturing tolerances, The value is required to be a negative value in the above range.
- the end first groove 202t may be one end first groove 202t positioned closest to the outer edge portion 123, or one or more end portions positioned near or near the outer edge portion 123.
- the first groove 202t may be used.
- FIG. 9 is an explanatory diagram showing an outline of a press machine for molding the anode separator 120 of the present embodiment shown in FIG.
- a press male mold Ku and a press female mold Kd are used.
- the press female die Kd includes a concave cavity into which each of the below-mentioned convex stripes of the press male die Ku enters, and is not different from the existing configuration.
- the press male mold Ku includes a first ridge Ts of a ridge adapted to the groove shape of the first groove 202 of the anode separator 120 and an end of the ridge adapted to the groove shape of the end first groove 202t.
- FIG. 10 is an explanatory diagram showing the relationship between the height of the unit cell 100 according to the present embodiment as viewed in cross section along the line 5-5 in the enlarged portion C of FIG.
- the end bottom wall 202ts of the end first groove 202t is smaller than the bottom wall 202s than the other first grooves 202 by a difference ⁇ H shown in the figure. is doing.
- each unit cell 100 receives fastening force at each part of the cell.
- the end bottom wall 202ts is in contact with the cathode separator 130 of the adjacent unit cell 100.
- the power generation region 112 (see FIGS. 2 to 3) of the MEGA 110 Contact of the outer edge 123 of the anode separator 120H to the peripheral edge, contact of the separator central region 121 to the power generation region 112 of the MEGA 110, and the bottom wall 202s and end of the first groove 202 to the cathode separator 130 of the other unit cell 100 Contact of the end bottom wall 202ts of the first groove 202t and contact of the leg 131 to the outer edge 123 of the other unit cell 100 occur.
- Such a contact state is continued while the fastening force is applied, and the fastening force is not only in the power generation region 112 of each unit cell having the anode separator 120H of the comparative example, but also in the region of the outer edge portion 123. It always extends.
- the anode-side separator 120H of the comparative example of FIG. 7 is equivalent to the end first groove 202t and the other first groove 202. Therefore, as described with reference to FIG. No measures are taken against the increase in thickness at the periphery of the power generation region 112 due to the presence of the sealing sheet 151 of the member 150. Therefore, in the anode-side separator 120H of the comparative example, the surface pressure locally increases at the periphery of the power generation region 112 surrounded by the dotted line in FIG. 6 due to the increase in the thickness described above, and the buckling and electrolyte of the MEA 110D are increased. It may cause damage to the membrane.
- the anode-side separator 120 of the present embodiment has an end first groove 202t extending on the outer edge 123 side, and an end side rising height Ht from the groove opening end of the end bottom wall 202ts is the other first height.
- the height is set to be lower than the rising height Hs of the groove 202 (difference ⁇ H ⁇ 0: see FIGS. 8 and 10). Therefore, according to the anode-side separator 120 of the present embodiment, the surface pressure applied to the flat outer edge 123 extending to the outer edge of the separator central region 121 is determined by the difference between the end-side rising height Ht and the rising height Hs. ⁇ H ( ⁇ 0) relaxes from the periphery of the other first groove 202 in the separator central region 121.
- anode-side separator 120 of the present embodiment a large surface pressure is applied to the separator central region 121 and the flat plate-like outer edge portion 123 extending to the outer edge in a state where the MEGA 110 is sandwiched between the cathode-side separator 130. Even if it is applied, buckling of the MEA 110D and damage to the electrolyte membrane can be avoided or suppressed by relaxing the surface pressure around the end first groove 202t extending on the outer edge 123 side.
- the end-side rising height Ht of the end first groove 202t may be set lower than the rising height Hs of the other first grooves 202, as shown in FIG.
- Lowering the protrusion height KHt of the end first ridge Tts can be easily achieved by the top polishing of the end first ridge Tts using a precision grindstone device.
- the separator manufacturing cost can be reduced, and the generation of excessive surface pressure that can occur when the fastening force reaches each part of the unit cell 100 and the accompanying MEA buckling and electrolyte.
- the problem of damage to both film surfaces of the film can be eliminated or suppressed by a simple technique of top polishing of the end first protrusion Tts in the press male mold Ku.
- the top polishing for the existing press male mold Ku is sufficient, the existing equipment can be used effectively, and the cost for manufacturing the separator can be further reduced due to the reduction of the mold cost.
- the occurrence of excessive surface pressure that can occur when the fastening force reaches each part of the unit cell 100 and the accompanying MEA buckling and damage to both membrane surfaces of the electrolyte membrane are as follows. This is caused by an accumulated error of each member such as the sealing sheet 151 of the gas flow path member 150 or a deviation of these members within the assembly accuracy.
- the anode-side separator 120 according to the present embodiment avoids or suppresses the above-described problems even when the accumulated error of each member or the deviation within the assembly accuracy occurs. For this reason, the manufacturing tolerance and assembly accuracy of each member can be relaxed to some extent, and therefore, the separator manufacturing cost and thus the fuel cell manufacturing cost can be further reduced through the reduction of the component manufacturing cost and the assembly cost.
- the fuel cell 10 of the present embodiment uses the anode side separator 120 that reduces the surface pressure around the end first groove 202t extending on the outer edge portion 123 side. Therefore, according to the fuel cell 10 of the present embodiment, since the local surface pressure is not increased during the power generation operation, buckling of the MEA 110D and damage to the electrolyte membrane can be avoided or suppressed, and the battery life can be reduced. In addition to extending the service life, battery performance can be maintained.
- the anode-side separator 120 in which the end-side rising height Ht of the end bottom wall 202ts of the end first groove 202t extending on the outer edge portion 123 side is lowered is used as an existing unit cell. 100 may be replaced. Therefore, according to the fuel cell 10 of the present embodiment, the manufacturing cost of the battery can be reduced, and the generation of the excessive surface pressure that can occur when the fastening force reaches each part of the unit cell 100 and the accompanying MEA seat. The problem of bending and damage to both membrane surfaces of the electrolyte membrane can be easily eliminated or suppressed.
- the present invention is not limited to the above-described embodiment, and can be realized with various configurations without departing from the spirit of the present invention.
- the technical features of the embodiments corresponding to the technical features in each embodiment described in the summary section of the invention are intended to solve part or all of the above-described problems, or part of the above-described effects. Or, in order to achieve the whole, it is possible to replace or combine as appropriate. Further, if the technical feature is not described as essential in the present specification, it can be deleted as appropriate.
- the left and right sides of the separator central region 121 are positioned on the upper and lower ends of the separator central region 121 in the first groove 202 provided in the separator central region 121 and on the outer edge portion 123 side.
- the first groove 202 extending in the direction is the end first groove 202t having a low end side rising height Ht, but is not limited thereto.
- the first groove 202 formed on the outer edge 123 side in the y direction in FIG. 3 may be the end first groove 202t having a low end side rising height Ht.
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Abstract
Description
Claims (5)
- 膜電極接合体に組み付けられる、第1の面と第1の面の裏面をなす第2の面とを有する燃料電池用セパレーターであって、
前記膜電極接合体の発電可能領域と対応する中央領域と、
前記中央領域から外縁に延びる平板状の外縁部と、
前記第1の面における、前記中央領域に形成されている第1面側凹溝部と、
前記第2の面における、前記中央領域に形成されている第2面側凹溝部とを備え、
前記第1面側凹溝部の溝と前記第2面側凹溝部の溝とは、前記中央領域に対するプレス成型による複数の凹凸条の形成により、前記中央領域において前記第1の面と第2の面に交互に並ぶと共に、前記第1面側凹溝部の内、前記膜電極接合体とは異なる他の部材の端部が位置し得る境界位置における前記第1面側凹溝部の底部壁は、他の前記第1面側凹溝部の底部壁よりも、凹溝開口端からの立ち上がり高さが低い
燃料電池用セパレーター。 - 請求項1に記載の燃料電池用セパレーターにおいて、
前記境界位置は、前記第1面側凹溝部の外縁部側に位置し、前記第1面側凹溝部の外縁部側における前記第1面側凹溝部の前記底部壁の立ち上がり高さが、前記他の前記第1面側凹溝部の底部壁よりも低い、燃料電池用セパレーター。 - 請求項2に記載の燃料電池用セパレーターにおいて、
前記第1面側凹溝部の外縁部側における前記第1面側凹溝部の前記底部溝の内、最も外縁部側に位置する前記第1面側凹溝部の前記底部壁の立ち上がり高さが、前記中央領域に位置する前記他の前記第1面側凹溝部の前記底部壁よりも低い、燃料電池用セパレーター。 - 膜電極接合体に組み付けられる、第1の面と第1の面の裏面をなす第2の面とを有する燃料電池用セパレーターであって、
前記膜電極接合体の発電可能領域と対応する中央領域と、
前記膜電極接合体の発電領域と対向するセパレーター中央領域から外縁に延びる平板状の外縁部と、
前記第1の面における、前記セパレーター中央領域において、一方の面の側に形成されているた第1面側凹溝部と、
前記第2の面における、前記セパレーター中央領域において、他方の面の側に形成されているた第2面側凹溝部とを備え、
前記第1面側凹溝部の溝と前記第2面側凹溝部の溝とは、前記セパレーター中央領域に対するプレス成型による複数の凹凸条の形成により、前記セパレーター中央領域において前記第1の面と第2の面にセパレーター表裏面で交互に並ぶと共に、前記第1面側凹溝部の内、最も外縁部側に位置する前記第1面側凹溝部の底部壁は、前記セパレーターの中央領域に位置する前記中央領域に位置するその他の前記第1面側凹溝部の底部壁よりも、凹溝開口端からの立ち上がり高さが低い、
燃料電池用セパレーター。 - 膜電極接合体を第1のセパレーターと第2のセパレーターで挟持する燃料電池セルを複数積層した燃料電池であって、
前記燃料電池セルのそれぞれは、請求項1から4のいずれかに記載の燃料電池用セパレーターを前記第1のセパレーターとして備え、前記外縁部は前記膜電極接合体の発電領域外部位に接合され、
隣り合って積層されている前記燃料電池セルにおいて、一の前記燃料電池セルの前記第1のセパレーターが有する前記第1面側凹溝部の底部壁は、他の前記燃料電池セルの前記第2のセパレーターに接触している、
燃料電池。
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CA2925249A CA2925249C (en) | 2013-10-01 | 2014-09-30 | Fuel cell separator and fuel cell |
KR1020167007946A KR101889201B1 (ko) | 2013-10-01 | 2014-09-30 | 연료 전지용 세퍼레이터 및 연료 전지 |
EP14850963.1A EP3054513B1 (en) | 2013-10-01 | 2014-09-30 | Fuel cell separator and fuel cell |
CN201480054180.XA CN105594038B (zh) | 2013-10-01 | 2014-09-30 | 燃料电池用分隔件及燃料电池 |
US15/022,050 US10153498B2 (en) | 2013-10-01 | 2014-09-30 | Fuel cell separator and fuel cell |
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US10629919B2 (en) | 2015-07-03 | 2020-04-21 | Lg Chem, Ltd. | Separating plate, method for manufacturing same, and fuel cell stack comprising same |
JP6177296B2 (ja) * | 2015-10-22 | 2017-08-09 | 本田技研工業株式会社 | 燃料電池 |
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JP2015069968A (ja) | 2015-04-13 |
KR20160047547A (ko) | 2016-05-02 |
EP3054513B1 (en) | 2018-07-04 |
JP6090091B2 (ja) | 2017-03-08 |
CA2925249A1 (en) | 2015-04-09 |
KR101889201B1 (ko) | 2018-08-16 |
US20160233522A1 (en) | 2016-08-11 |
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CN105594038B (zh) | 2017-12-01 |
EP3054513A1 (en) | 2016-08-10 |
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