CN101281969B - Composite porous body, gas diffusion layer member, cell member, and manufacturing method thereof - Google Patents
Composite porous body, gas diffusion layer member, cell member, and manufacturing method thereof Download PDFInfo
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- CN101281969B CN101281969B CN2008100967118A CN200810096711A CN101281969B CN 101281969 B CN101281969 B CN 101281969B CN 2008100967118 A CN2008100967118 A CN 2008100967118A CN 200810096711 A CN200810096711 A CN 200810096711A CN 101281969 B CN101281969 B CN 101281969B
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- porous body
- conductivity porous
- diffusion layer
- gas diffusion
- resin
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Images
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Fuel Cell (AREA)
Abstract
A composite porous body, a gas diffusion layer member of a polymer electrolyte fuel cell, a cell member for the polymer electrolyte fuel cell, and manufacturing methods thereof are provided. The composite porous body is a metallic composite porous body in which a sheet-like metal portion composed of a composite porous body having a three-dimensional mesh structure and a resin portion extending in an in-plane direction of the metal portion are integrally formed with each other. The gas diffusion layer member of a polymer electrolyte fuel cell is composed of a composite porous body in which a sheet-like metal portion composed of a composite porous body having a three-dimensional mesh structure and a resin portion extending in an in-plane direction of the metal portion are integrally formed with each other. Also, the gas diffusion layer member of a polymer electrolyte fuel cell has a separator plate, and the conductive porous body placed on at least one surface of the separator plate. A resin frame is integrally provided so as to cover the peripheries of separator plate and the conductive porous body.
Description
The application is an application number: 200480012727.6, the applying date: the dividing an application of the application for a patent for invention of on May 7th, 2004, denomination of invention " composite porous body, gas diffusion layer member, cell member and manufacture method thereof ".
Technical field
The present invention relates to gas diffusion layer member, use in solid polymer fuel cell cell member and the manufacture method thereof of a kind of composite porous body, polymer electrolyte fuel cell.
Background technology
Have the laminar conductivity porous body of three dimensional network ocular structure, be applicable to the gas diffusion layer member of filter, radiating component, suction member and polymer electrolyte fuel cell etc., be suitable for, be provided in the various devices with multiple use.But this conductivity porous body generally has shortcomings such as intensity is low, yielding, therefore, is all pointed out always, the conductivity porous body is difficult to be installed in the difficulty of its operations such as device.Have in the mechanism that proposes in order to address these problems: for example, shown in the patent documentation 1 (with reference to Japanese kokai publication sho 48-13956 communique), the formation of filling different material in the end of conductivity porous body and strengthening and, shown in the patent documentation 2 (with reference to Japanese kokai publication hei 08-53723 communique), in order to form device erection opening etc. at the conductivity porous body, in the pore of conductivity porous body, fill solids such as metal or plastics, and the formation of the part that strengthens its intensity is set.
And, utilize the polymer electrolyte fuel cell of gas diffusion layer member, with the power supply of family's dedicated fixed formula power supply and electric car, or the small-sized power supply that carries machine, quite paid close attention to.Have in this polymer electrolyte fuel cell, as for one of structure of connecting a plurality of cells unit successively, with the cell cells overlap, so-called eclipsed form is (for example, with reference to patent documentation 3: Japanese kokai publication hei 08-78028 communique).
Recently, along with the utilization of solid macromolecule electrolyte, carrying out the exploitation of portable small-sized polymer electrolyte fuel cell.Usually, because in polymer electrolyte fuel cell, the electromotive force that pair of electrodes (cell unit) is produced is less, therefore adopted structure with a plurality of cell units in series.But, if adopt stack, must arrange dividing plate between each the cell unit that then piles up, and be necessary to carry methanol aqueous solution or air, and be necessary auxiliary machinery such as pump to the narrowed flow path of piling up.So, all unfavorable at aspects such as volume, weight, expenses.So, carry out, do not utilize dividing plate, connect by the cell unit that is arranged side by side in the plane, seek space-saving, the exploitation of so-called plane.
Flat fuel cell, what propose has: for example, between fuel electrodes and air pole, constitute the cell unit of clamping dielectric substrate, and on the opposite of the dielectric substrate of each cell monoreactant utmost point and air pole, layout has the connecting plate of through hole, thereby connect mutual neighbour's the cell monoreactant utmost point and the formation of air pole successively (for example, with reference to patent documentation 4: TOHKEMY 2002-56855 communique) by connecting plate.
And the electrode of polymer electrolyte fuel cell (cell unit) for example is fabricated to basic composite component: have dielectric substrate; A pair of (2) planar electrode in the two sides of dielectric substrate adjacency; Be arranged at around these dielectric substrates and the electrode, keep the bubble-tight sealing of dielectric substrate and electrode.(for example, with reference to patent documentation 5: TOHKEMY 2002-280025 communique)
Patent documentation 5 TOHKEMY 2002-280025 communiques
But, in above-mentioned patent documentation 1,2 described formations, in the pore of conductivity porous body, fill foreign material, and distortion has the conductivity porous body pore of three dimensional network ocular structure, with this part as reinforcing section, strengthen the rigidity of conductivity porous body, therefore, effective usable floor area of conductivity porous body just will reduce.So, for remedy the such use that is the conductivity porous body decide the reduction of function, or the method that adopts for the above-mentioned minimizing part of replenishing conductivity porous body pore has produced the new problems such as maximization that cause the conductivity porous body again.And, in the conductivity porous body, fill different materials because be, resin etc. for example, and this part is assigned to improve the formation of conductivity porous body rigidity as rib, so, use through hole if wear the device installation, then be difficult to realize high-precision processing, for example expose the processing such as end of conductivity porous body at the inner peripheral surface of this through hole at its reinforcing section.
And, in the patent documentation 3 described formations, be arranged in the dividing plate between each the cell unit that piles up, be provided with for groove to gas diffusion layers fuel supplying (hydrogen) and air (oxygen).Because of this groove needs volume, the weight of certain thickness dividing plate, the miniaturization and of fuel cell is hindered.
And the conductivity porous bodies such as carbon steel coupon of formation gas diffusion layers have character such as intensity is low, yielding, and therefore problems such as bringing difficulty when being difficult to operation, manufacturing fuel cell is arranged.
And, in the patent documentation 4 described formations, at first form a plurality of with the incorporate cell of air seal portion, fuel electrodes and air pole unit, again that the monomer whose battery unit is placed side by side at certain intervals on the plane, and arrange successively below the side with adjacent cell unit and the surperficial Z font connecting plate that is connected of opposite side, also must carry out between the slit between the connecting plate more operations such as filling sealing agent, and assembled component is also a lot, therefore on making, acquires a certain degree of difficulty.
And, realize that fuel cell more during miniaturization, in the micro gap that has between the cell unit of sandwich construction, is difficult to abundant filling sealing agent, and because of sealant loading deficiency, and might produce the problems such as not good or liquid fuel leakage that insulate between battery unit.In addition, in the patent documentation 4 described formations, constitute the conductivity porous bodies such as carbon steel coupon of gas diffusion layers, have low, the yielding character of intensity, therefore problems such as bringing difficulty when being difficult to operation, manufacturing fuel cell is arranged.
And, in the patent documentation 5 described formations, have if a plurality of cells unit will be connected successively, then the cell cells overlap, between each cell unit, place the stack of dividing plate.
But, if will utilize compound substantially key element to constitute stack fuel cell with dielectric substrate and the sealing of electrode one, then must arrange respectively for gas diffusion layers to each electrode fuel supplying or air (oxygen), and, also must between each overlapping cell unit, arrange dividing plate, therefore, dividing plate shared volume and weight in whole fuel cell will become big.
And, owing to be necessary to carry fuel such as methanol aqueous solution or air, need auxiliary machineries such as pump to overlapping narrowed flow path, therefore, it is unfavorable that aspects such as volume, weight, expense all become.And, during with a plurality of basic complex factors, gas diffusion layers and dividing plate assembling, must guarantee the sealing between each member.Therefore, be necessary to develop a kind of easy to manufacture, fuel cell with better productive structure.
Summary of the invention
The present invention carries out in view of the above problems, and its purpose is: a kind of effective usable floor area that can guarantee the conductivity porous body is provided, can improves the composite porous body and the manufacture method thereof of its operability again; Provide a kind of structure simple and can miniaturization and fuel cell easy to manufacture, that can supply high efficiency electric power; A kind of formation with compactness also is provided, can connects a plurality of cells unit and cell member miniaturization and, that productivity is superior of realization fuel cell.
In order to achieve the above object, the composite porous body relevant with the invention of technical scheme 1 is characterized in that, have the three dimensional network ocular structure laminar conductivity porous body and, the resin portion to the face direction of this conductivity porous body prolongs forms as one.
And the composite porous body relevant with the invention of technical scheme 2 is characterized in that, contains inorganic filler in above-mentioned resin portion.
According to the invention of technical scheme 1,2,, can strengthen the conductivity porous body, and can improve its operability owing to be provided with above-mentioned resin portion in the outer peripheral edges of above-mentioned conductivity porous body.In addition, since resin portion from the outer peripheral edges of conductivity porous body just as prolonging to the face direction highlightedly, so, to in composite porous body, wear the part of device erection opening, can be defined in this resin portion, and can be easily, wear the device erection opening with high accuracy, simultaneously, can also control the minimizing of effective usable floor area of conductivity porous body to greatest extent.Especially, when resin portion contains inorganic filler, realize the high strength of above-mentioned resin portion itself, can improve the intensity of composite porous body thus, thereby improve its operability more.
And, the position of resin portion is set, not only be defined in the whole edge of conductivity porous body, also be not limited to the outer edge, according to necessity, can partly cut setting as required.And, connect a plurality of conductivity porous bodies in resin portion and constitute also passable.
The composite porous body relevant with the invention of technical scheme 3 is characterized in that, above-mentioned inorganic filler is fibrous, and simultaneously, the content in above-mentioned resin portion is more than the 5wt% of this resin portion, below the 60wt%.
According to the invention of technical scheme 3, can be well and positively realize the high strength of resin portion itself.
The gas diffusion layer member of the polymer electrolyte fuel cell relevant with the invention of technical scheme 4 is made of each described composite porous body in the technical scheme 1～3.
The invention of technical scheme 5 is, the gas diffusion layer member of technical scheme 4 described polymer electrolyte fuel cells is characterized in that, above-mentioned resin portion is the resin frame of surrounding around the above-mentioned conductivity porous body.
Invention according to technical scheme 4,5 utilizes composite porous body, can constitute the gas diffusion layer member of polymer electrolyte fuel cell.
The invention relevant with technical scheme 6 is, the gas diffusion layer member of technical scheme 5 described polymer electrolyte fuel cells, it is characterized in that, be provided with from the outstanding terminal joint of above-mentioned conductivity porous body, and terminal is exposed to the outside of above-mentioned resin frame with joint.
The invention relevant with technical scheme 7 is that the gas diffusion layer member of technical scheme 6 described polymer electrolyte fuel cells is characterized in that, a plurality of above-mentioned conductivity porous bodies are arranged side by side, and is provided with above-mentioned resin frame around it.
According to the invention of technical scheme 6,7, be because of conductivity porous body from hold concurrently gas diffusion layers and collector body, make terminal outstanding, with its simple formation of resin frame encirclement, so easy to manufacture with joint.And, utilize this gas diffusion layer member, side at the conductivity porous body forms catalyst layer, and make be provided with catalyst layer in the face of to 2 gas diffusion layer members between arrange dielectric film, only engage these, can realize being undertaken the cell unit of the air seal of end face easily by resin frame by hot pressing etc.
And, if adopt have a plurality of conductivity porous bodies and terminal joint placed side by side in the plane, and be arranged at the structure that its resin frame is on every side kept each conductivity porous body simultaneously, then only carry out catalyst layer formation and hot pressing etc. and engage operation, insulation each other, and can be easy to realize so-called plane battery unit side by side, plane, a plurality of cells unit.
And, the terminal joint, as long as on the surface (top and bottom) of resin frame or arbitrary position of side etc. expose.For example, be embedded under the state in the resin frame with integral body, the formation of exposing at front end only, or only expose at arbitrary place of top and bottom, and the formation that does not expose the side etc. are also passable.
The invention relevant with technical scheme 8 is, the gas diffusion layer member of technical scheme 5 described polymer electrolyte fuel cells, it is characterized in that, in above-mentioned resin frame, be provided with the first fluid service duct that is connected as the gas-diffusion electrode of electrode surface with the one side of above-mentioned conductivity porous body and first fluid discharge-channel with, the second fluid service duct and second fluid drainage channel that are not connected with its gas-diffusion electrode.
The invention relevant with technical scheme 9 is, the gas diffusion layer member of technical scheme 8 described polymer electrolyte fuel cells, it is characterized in that, above-mentioned first fluid service duct and above-mentioned first fluid discharge-channel, the above-mentioned second fluid service duct and above-mentioned second fluid drainage channel are to run through 4 through hole settings of above-mentioned resin frame.
The invention relevant with technical scheme 10 be, the gas diffusion layer member of technical scheme 9 described polymer electrolyte fuel cells is characterized in that, in above-mentioned each through hole every any two are separately positioned on the line symmetry.
The invention relevant with technical scheme 11 is, have that more than one technical scheme 8～10 described above-mentioned gas diffusion layer members are arranged in outside in the dielectric substrate that is made of solid macromolecule electrolyte respectively and the polymer electrolyte fuel cell of the cell unit that constitutes, it is characterized in that, in the above-mentioned cell unit, be provided with: the fuel-side service duct makes the above-mentioned first fluid service duct that is arranged at above-mentioned gas diffusion layer member one side and is arranged at the above-mentioned second fluid service duct connection that above-mentioned gas spreads the layer member opposite side; The oxygen side service duct makes the above-mentioned second fluid service duct that is arranged at above-mentioned gas diffusion layer member one side and is arranged at the above-mentioned first fluid service duct connection that above-mentioned gas spreads the layer member opposite side; The fuel-side discharge-channel makes the above-mentioned first fluid discharge-channel that is arranged at above-mentioned gas diffusion layer member one side and is arranged at above-mentioned second fluid drainage channel connection that above-mentioned gas spreads the layer member opposite side; The oxygen side discharge-channel makes above-mentioned second fluid drainage channel that is arranged at above-mentioned gas diffusion layer member one side and is arranged at the above-mentioned first fluid discharge-channel connection that above-mentioned gas spreads the layer member opposite side.
According to the invention of technical scheme 8, owing to strengthening by resin frame around the low porous gas diffusion electrode of intensity, so during manufacturing, operation becomes easily, and can realize the fuel cell that productivity is high to technical scheme 11.And, for dielectric substrate, can the adhering resin frame, therefore, its sealing becomes well, and can effectively prevent the leakage of the fuel of fuel cell, thus but efficient provision fuel.
And, because the conductivity porous body has the three dimensional network ocular structure, therefore, fluids such as fuel or air, diffusion is supplied in the electrolyte-catalyst agent interface of generating electrodes reaction equably.
And, with the gas diffusion layer member among the present invention, a plurality of piling up, and when constituting fuel cell, each through hole can be communicated with respectively, and form easily fluid service duct or the fluid drainage channel that the thickness direction to gas diffusion layer member prolongs, thereby can realize to supply the fuel cell of high efficiency fuel.
And, utilize through hole of the present invention to be arranged on gas diffusion layer member on the line symmetry, differently pile up inside and outside then only making, the utmost point just can act as a fuel gas diffusion layer member one side, opposite side forms the fluid service duct and the fluid drainage channel of 2 systems of any in fuel electrodes and the air pole that are communicated in as air pole.Thereby, can realize that member is few, constitute the fuel cell simple, that productivity is high.
The invention relevant with technical scheme 12 is, the gas diffusion layer member of technical scheme 4 described polymer electrolyte fuel cells, it is characterized in that, has clathrate frame portion, this clathrate frame portion comprises: the oxygen diffusion electrode, with the one side of above-mentioned conductivity porous body as oxygen supply face, another side as electrode surface; Resin portion, the non-conductive material of both sides constitutes by being arranged in the above-mentioned oxygen diffusion electrode sidepiece at least; Peristome is arranged at oxygen supply face side, is connected with above-mentioned resin portion, makes above-mentioned oxygen supply open towards the outside.
According to the invention of technical scheme 12, so-called gas diffusion layers and collector plate because the oxygen diffusion electrode is held concurrently so it constitutes merely, can be realized the miniaturization of fuel cell.And, strengthen the oxygen diffusion electrode by resin portion and clathrate frame portion, so its operability is good, and can improve the productivity of fuel cell.And, owing to connecting, these resin portion and clathrate frame portion be integrally formed at the oxygen diffusion electrode, so can save the arduous of a plurality of members of airtight assembling, can improve the productivity of fuel cell.
The invention relevant with technical scheme 13 is, the gas diffusion layer member of technical scheme 12 described polymer electrolyte fuel cells, it is characterized in that, above-mentioned oxygen diffusion electrode is provided with to cut apart a plurality of ground mode, is provided with the connection box that is made of non-conductive material that connects between each oxygen diffusion electrode.
According to the invention of technical scheme 13, owing to possess a plurality of oxygen diffusion electrodes, so can produce a plurality of electrodes easily side by side and the flat fuel cell of the formation of series connection to the face direction at a gas diffusion layer member.
The invention relevant with technical scheme 14 be, the gas diffusion layer member of technical scheme 12 or technical scheme 13 described polymer electrolyte fuel cells is characterized in that, above-mentioned clathrate frame portion is made of non-conductive material.
According to the invention of technical scheme 14, because clathrate frame portion is non-conductive, so, even when the oxygen diffusion dividing electrodes is a plurality of, can not cause short circuit phenomenon between each oxygen diffusion electrode yet, can protect the oxygen supply face.
The invention relevant with technical scheme 15 is, the gas diffusion layer member of technical scheme 12 or technical scheme 13 described polymer electrolyte fuel cells, it is characterized in that, above-mentioned clathrate frame portion is made of conductive material, thereby it is provided with to cut apart a plurality of ground mode corresponding to a plurality of above-mentioned oxygen diffusion electrodes.
Invention according to technical scheme 15; because the clathrate frame partly cuts and is arranged at each oxygen diffusion electrode, therefore, for example selects high strength components such as conductive metal mesh screen for use with clathrate frame portion; the oxygen diffusion electrode is short-circuited mutually, and protection oxygen supply face.
The invention relevant with technical scheme 16 is, the gas diffusion layer member of technical scheme 4 or technical scheme 5 described polymer electrolyte fuel cells, it is characterized in that, be provided with to have the collector body of the two-dimensional mesh ocular structure that prolongs to the face direction on above-mentioned conductivity porous body surface.
Invention according to technical scheme 16, because the outer peripheral edges at the conductivity porous body are formed with resin portion at least, therefore can seek the raising of the operability of this gas diffusion layer member, and can utilize this gas diffusion layer member, the minimizing in the assembling man-hour when seeking the assembling solid high molecular fuel battery, and can seek the raising of assembly precision.
And because resin portion in the outer peripheral edges of conductivity porous body, along the setting of whole edge, therefore, is for example only processed resin portion at least, easily applicator is fixing with shapes such as holes.And because collector body has the two-dimensional mesh ocular structure that prolongs to the face direction, therefore, the electric current that can produce from polymer electrolyte fuel cell by collector body, conducts well to this face direction.
And, not only in the outer peripheral edges of conductivity porous body, but also in the formation that the outer peripheral edges of collector body also form as one, can the surface of each subtend be connected to each other much at one.Thereby, can reduce the resistance between conductivity porous body and the collector body to greatest extent.
The invention relevant with technical scheme 17 be, the gas diffusion layer member of technical scheme 16 described polymer electrolyte fuel cells is characterized in that, above-mentioned collector body has at least a part to infiltrate in the surface of above-mentioned conductivity porous body.
According to the invention of technical scheme 17, owing to the part that has at least of collector body, infiltrate in conductivity porous plastid surface, therefore can realize the good state that is electrically connected between conductivity porous plastid and the collector body.And because collector body has the two-dimensional mesh ocular structure that prolongs to the face direction, therefore, the electric current that can produce from polymer electrolyte fuel cell by this collector body, and conducts well to the face direction.
By above constituting, can realize little, the high-power polymer electrolyte fuel cell of resistance.
And, at least the outer peripheral edges at the conductivity porous body are formed with resin portion, therefore can seek the raising of the operability of this gas diffusion layer member, and can utilize this gas diffusion layer member, in the time of the minimizing in the assembling man-hour when seeking the assembling solid high molecular fuel battery, and can seek the raising of assembly precision.Particularly, resin portion not only in the outer peripheral edges of conductivity porous body, but also in the formation that the outer peripheral edges of collector body also form as one, can be these conductivity porous body and collector body, make the surface of subtend interconnected much at one, simultaneously, can also keep this connection status for a long time.Thereby, collector body infiltrate in the surface of conductivity porous body and, the resistance between conductivity porous body and the collector body can be reduced to greatest extent, and when can seek the high powerization of further polymer electrolyte fuel cell, the long lifetime of this battery can also be sought.
The invention relevant with technical scheme 18 is, a kind of gas diffusion layer member of polymer electrolyte fuel cell, it is characterized in that, have dividing plate and be arranged on dividing plate at least the one side above-mentioned conductivity porous body, and be integrally formed with aforementioned barriers and cover above-mentioned conductivity porous body around resin frame.
According to the invention of technical scheme 18, owing to become one, so processing ease by resin frame, the breakage of the gas diffusion layer member when preventing to make fuel cell, and can realize the fuel cell of high productivity.And, because the side of conductivity porous body is capped by resin frame, thus be closed to the open pores of lateral opening, thus can effectively prevent fuel leak.And, because the runner of fluid (fuel or air etc.) is formed in the gas-diffusion electrode of conductivity porous body, therefore unnecessaryly become runner such as groove in shelf-shaped, and can utilize way-board and can seek the miniaturization and of fuel cell.
And, in the gas diffusion layer member among the present invention, be provided with and make first flow that first fluid passes through and be advisable for second runner that second fluid is passed through.This first and second runner is formed on resin frame and is advisable.And first and second runner is set to be connected in the oxygen diffusion electrode and runs through resin frame and is advisable.
The invention relevant with technical scheme 19 is, the gas diffusion layer member of technical scheme 18 described polymer electrolyte fuel cells is characterized in that, is provided with in the above-mentioned resin frame, make first fluid runner that first fluid passes through and, second fluid course that second fluid is passed through.
According to the invention of technical scheme 19, to each gas-diffusion electrode, various different fluid (fuel and air) are passed through from the outside of gas diffusion layer member, and it produce electrode reaction.This first and second runner, though with the different shape setting, but if its placement is a resin frame, handling ease then, and, general, compared with being processed to form in the conductivity porous body of high price, favourable aspect expense, simultaneously, can effectively utilize the surface of the conductivity porous body relevant with the electrical efficiency of electrode.And, make this first and second runner be set to run through resin frame and be provided with, so, gas diffusion layer member piled up and when constituting fuel cell, can form the runner that is communicated with to thickness direction easily, thus fuel cell that can implementation structure is simple, productivity is high.
The invention relevant with technical scheme 20 is, polymer electrolyte fuel cell, it is characterized in that, technical scheme 18 or technical scheme 19 described gas diffusion layer members, overlapping to the thickness direction multilayer, and be furnished with the dielectric substrate that constitutes by solid macromolecule electrolyte between each gas diffusion layer member, simultaneously, possess the catalyst layer on the interface of the above-mentioned oxygen diffusion electrode that is arranged at this dielectric substrate and each gas diffusion layer member.
According to the invention of technical scheme 20, polymer electrolyte fuel cell of the present invention can simple formation form the cell unit by the structure of arranging dielectric substrate and catalyst layer between 2 gas diffusion layer members.And, if a plurality of gas diffusion layer members are piled up, between each member, arrange dielectric substrate respectively, then can form the stack fuel cell of piling up a plurality of cells unit easily.
The invention relevant with technical scheme 21 is that the use in solid polymer fuel cell cell member is characterized in that, has: dielectric substrate; Between this dielectric substrate, get involved catalyst layer, and clamp at least one pair of above-mentioned conductivity porous body of this dielectric substrate; Surround this conductivity porous body around and the resin frame that prolongs to the face direction.
The invention relevant with technical scheme 23 be, technical scheme 21 or technical scheme 22 described use in solid polymer fuel cell cell members is characterized in that, above-mentioned resin frame, surround above-mentioned conductivity porous body and above-mentioned dielectric substrate around and be provided with.
Invention according to technical scheme 21 to 23, gas diffusion layers and collector component because the conductivity porous body is held concurrently, therefore, not only can be little with thickness, simple formation, the high cell unit of realization current collecting efficiency, and, even without the auxiliary equipment such as pump of transfer the fuel or air, also can be to all conductivity porous body (gas diffusion layers) effective supply fuel (hydrogen) or air (oxygen).And, adopt to have many formations to the conductivity porous body, thereby only by each electrode is connected successively, promptly can be with a plurality of cell units in series.
And, in order to interconnect the terminal of electrode, as long as be exposed in the surface (top and bottom) of resin frame or the side arbitrary position so that can be connected with other terminals or external circuit, for example, whole terminal is embedded under the state of resin frame, only expose the formation of front end or only be exposed to either side in the above and below, but the formation of not exposing in the side; Or be embedded in the resin frame, and be exposed to the formation of the through hole inner peripheral surface that runs through resin frame and terminal can.And, if can directly connect up, then terminal need not be set separately at the conductivity porous body.
And, resin frame be set to just as surround the conductivity porous body around and dielectric substrate around, then can make the operability of cell member better.
Technical scheme 24 of the present invention is, the manufacture method of composite porous body, it is characterized in that: with above-mentioned conductivity porous body as built in items, be shaped just as the embedding of the edge sprayed resin that is connected in this conductivity porous body by carrying out, and produce each described composite porous body in the technical scheme 1～3.
According to the invention of technical scheme 24, owing to form composite porous body, therefore can form resin portion with high accuracy by embedding to be shaped, simultaneously, also be easy to form this composite porous body.And, the part that is connected with resin portion at the conductivity porous body, owing to molten resin infiltrates in solidifying in the pore of the side mouth of conductivity porous body, therefore, more firmly be connected with resin portion by grappling effect (anchoring effect) metal part, and can realize the porous body of composite metal that intensity is high.And, if resin portion contains inorganic filler, when embedding shaping, from pore to the outer peripheral edges opening of conductivity porous body, inside to this conductivity porous body, have molten resin to want excessive flow fashionable, inorganic filler is wrapped in the mesh of dividing this pore, and just dwindles at the aperture area of the above-mentioned pore of the outer peripheral edges of conductivity porous body.Therefore, when above-mentioned embedding is shaped,, can control the minimizing of effective usable floor area of conductivity porous body to greatest extent because of controlling the influx of molten resin to the inside of conductivity porous body.
And, as mentioned above, when carrying out above-mentioned embedding shaping, because inorganic filler is wrapped in the mesh of division to the pore of the outer peripheral edges opening of conductivity porous body, therefore, molten resin is with the sclerosis of this state, though and the inflow to the inside of conductivity porous body of molten resin is suppressed to greatest extent, can also realize the firm joint of resin portion and conductivity porous body.
The invention relevant with technical scheme 25 is, the manufacture method of the gas diffusion layer member of polymer electrolyte fuel cell, it is characterized in that: with above-mentioned conductivity porous body as built in items, be shaped just as the embedding of the edge sprayed resin that is connected in this conductivity porous body by carrying out, and produce technical scheme 4 or technical scheme 5 described gas diffusion layer members.
Invention according to technical scheme 25, owing to molten resin infiltrates in solidifying in the pore of conductivity porous body side mouth, therefore, when can effectively guarantee the air seal of conductivity porous body, by the grappling effect, can firmly connect conductivity porous body and resin frame.And, with a plurality of conductivity porous bodies side by side, sprayed resin around it and shaping resin frame, thereby can make have a plurality of cells unit carry out the gas diffusion layer member that the plane battery unit is made easily.
In this manufacture method, when terminal being set using joint, form resin frame after, by methods such as plating, evaporation, spraying platings, can on resin frame, form.Perhaps, at the integrally formed terminal joint of conductivity porous body, it is also passable that these conductivity porous bodies and terminal are embedded shaping with joint as built in items.
Form when forming terminal after the resin frame and use joint, can be between molding die clamping conductivity porous body and in above-mentioned conductivity porous body sprayed resin on every side.And, forming terminal with the conductivity porous body of joint during as built in items, can will be held between the mould and sprayed resin with connector clamp from the outstanding terminal of conductivity porous body.And, in this manufacture method,, can spray terminal that formation is made of electroconductive resin with joint and the resin frame that constitutes by non-conductive resin by so-called double-colored shaping.
The invention relevant with technical scheme 26 is, the manufacture method of the gas diffusion layer member of polymer electrolyte fuel cell, it is characterized in that: with above-mentioned conductivity porous body as built in items, by edge and oxygen supply face sprayed resin to above-mentioned conductivity porous body, and produce integrally formed resin portion and clathrate resin portion, technical scheme 12 described gas diffusion layer members.
Invention according to technical scheme 26, the part that the resin that is to spray is connected with gas-diffusion electrode, owing to infiltrating in the pore of opening to the surface of conductivity porous plastid, molten resin solidifies, therefore, gas-diffusion electrode firmly is connected with the resin part by the grappling effect, and can provide intensity high gas diffusion layer member.
The invention relevant with technical scheme 27 is, the manufacture method of the gas diffusion layer member of technical scheme 16 or technical scheme 17 described polymer electrolyte fuel cells, it is characterized in that: will on the surface of above-mentioned conductivity porous body, arrange above-mentioned collector body and the laminated body that constitutes as built in items, be arranged in this built in items on the die face, fixing by these die face to the thickness direction compression of above-mentioned laminated body, simultaneously, form die cavity the matched moulds operation and, after treating that this matched moulds operation finishes, spray molten resin to above-mentioned die cavity, therefrom on the outer peripheral edges of above-mentioned laminated body along whole edge the integrally formed resin portion that prolongs to the face direction.
According to the invention of technical scheme 27, can form gas diffusion layer member integrally formed by conductivity porous body, collector body and resin portion and the polymer electrolyte fuel cell that constitutes well.Especially, in the matched moulds operation, by die face with above-mentioned built in items after the compression of this thickness direction is fixing, with this state, in die cavity, spray molten resin, therefore, can make die face and above-mentioned built in items fluid-tight engagement.Thereby, can suppress to have between die face, conductivity porous body and the collector body molten resin to flow into, simultaneously, also can suppress the position deviation of the above-mentioned built in items that molten resin takes place at die cavity internal cause expulsion pressure.Thereupon, can reliably form this gas diffusion layer member with high accuracy.And, owing to when matched moulds, collector body is infiltrated in the surface of conductivity porous plastid, therefore, during injection, can realize the fluid-tight engagement state on die face and above-mentioned built in items surface.Thereby, can reliably realize the good state that is electrically connected of collector body and conductivity porous plastid, simultaneously, can also not cause the defective in the manufacturing and form gas diffusion layer member with high accuracy.
In addition, the part that is connected with resin portion at the conductivity porous body, owing to molten resin infiltrates in solidifying in the pore of the side mouth of conductivity porous body, therefore, above-mentioned conductivity porous body can firmly be connected with resin portion by the grappling effect.Therefore, if resin portion is not only in the outer peripheral edges of above-mentioned conductivity porous body, but also form as one in the outer peripheral edges of collector body, then can seek the high strength that is connected and the long lifetime of each member of the gas diffusion layer member that constitutes by conductivity porous body, collector body and resin portion.
The invention relevant with technical scheme 28 is, the manufacture method of use in solid polymer fuel cell cell member, it is characterized in that: with above-mentioned dielectric substrate and, at least one pair of above-mentioned conductivity porous body of getting involved above-mentioned catalyst layer and clamp this dielectric substrate between this dielectric substrate is as built in items, be shaped just as the be shaped embedding of above-mentioned resin frame of the edge part sprayed resin that is connected in above-mentioned conductivity porous body by carrying out, and produce each described cell member in the technical scheme 21～23.
The invention relevant with technical scheme 29 is, the manufacture method of technical scheme 28 described use in solid polymer fuel cell cell members, it is characterized in that: with above-mentioned dielectric substrate and above-mentioned conductivity porous body, getting involved each other under the state of above-mentioned catalyst layer, embed when being shaped hot press.
Invention according to technical scheme 28,29, because molten resin infiltrates in solidifying in the pore of the side mouth of conductivity porous body, and dielectric substrate, catalyst layer and conductivity porous body are integrated, therefore, can guarantee the sealing of fuel gas and fuel liquid, simultaneously, can also be by the grappling effect, make that conductivity porous body and resin frame are firm to be connected.
And,, reserve certain intervals and arrange the conductivity porous body many, sprayed resin around it and shaping resin frame, and easily produce the plane cell member that one has a plurality of cells unit.And, dielectric substrate and conductivity porous body, by when embedding shaping, carrying out hot press, can be with integrally formed at the state of getting involved catalyst layer each other.
In this manufacture method, when terminal is arranged at conductivity porous body and complicated variant, form after the resin frame, by methods such as plating, evaporation, spraying platings, can on resin frame, form.Perhaps, at the integrally formed terminal of conductivity porous body, and these conductivity porous bodies and terminal are embedded shaping as built in items also passable.
And, the conductivity porous body of terminal that is fixed with other members during as built in items, is produced position deviation in order to prevent that the conductivity porous body from pressing because of sprayed resin, can use fixed terminal parts such as pin.And, the conductivity porous body is clamped between the molding die, then can not stay the maintenance vestige of any pin, form and surround conductivity porous body resin frame on every side.In addition, in this manufacture method,, can spray terminal that formation is made of electroconductive resin and the resin frame that constitutes by non-conductive resin by so-called double-colored shaping.
The invention relevant with technical scheme 30 is, the manufacture method of the gas diffusion layer member of polymer electrolyte fuel cell, it is characterized in that: on the surface of above-mentioned conductivity porous body, arrange aforementioned barriers and the laminated body that constitutes as built in items, by carrying out the embedding shaping just as the edge part sprayed resin that is connected in this laminated body, each described above-mentioned gas spreads layer member in the technical scheme 18～20 and produce.
According to the invention of technical scheme 30, polymer electrolyte fuel cell of the present invention can constitute formation cell unit with the simple parts of only arranging dielectric substrate and catalyst layer between 2 gas diffusion layer members.And, if a plurality of gas diffusion layer members are piled up, between each member, arrange dielectric substrate respectively, then can form the stack fuel cell of piling up a plurality of cells unit easily.
In addition, the representational fuel that is used in above-mentioned polymer electrolyte fuel cell has two kinds of hydrogen and methanol aqueous solutions.When adopting methanol aqueous solution, though the fuel that trickles in the conductivity porous body is liquid, this part is called as gas diffusion layers by convention.Among the present invention, comprising the situation of utilizing liquid fuel, be called gas diffusion layers by convention, is not to be defined in gaseous fuel to use.
Description of drawings
Fig. 1 is the plane graph of expression according to the composite porous body of the embodiment of the invention 1.
Fig. 2 is the ideograph that the method for porous body shown in Figure 1 is made in expression.
Fig. 3 is the ideograph of expression according to the manufacture method of the composite porous body of the embodiment of the invention 1.
Fig. 4 is the schematic diagram of expression according to the demonstration test result of the action effect of the composite porous body of the embodiment of the invention 1 and manufacture method thereof.
Fig. 5 is the oblique view of expression according to the gas diffusion layer member of the embodiment of the invention 2.
Fig. 6 is the oblique view of expression according to another execution mode of the gas diffusion layer member of embodiments of the invention 2.
Fig. 7 is the oblique view of expression according to another execution mode of the gas diffusion layer member of embodiments of the invention 2.
Fig. 8 is the oblique view of expression according to another execution mode of the gas diffusion layer member of embodiments of the invention 2.
Fig. 9 is the oblique view of expression according to another execution mode of the gas diffusion layer member of embodiments of the invention 2.
Figure 10 is the oblique view of expression according to another execution mode of the gas diffusion layer member of embodiments of the invention 2.
Figure 11 is the oblique view of expression according to another execution mode of the gas diffusion layer member of embodiments of the invention 2.
The ideograph of the device that Figure 12 is utilized when being the conductivity porous body of representing to make among the present invention.
Figure 13 is the oblique view of explanation according to the manufacture method of the gas diffusion layer member of embodiments of the invention 2.
Figure 14 is the ideograph of expression manufacturing according to the reaction-injection moulding mould of the gas diffusion layer member of the embodiment of the invention 2.
Figure 15 is the plane graph of expression according to the gas diffusion layer member (fuel electrodes is used) of the embodiment of the invention 3.
Figure 16 is the plane graph of expression according to the gas diffusion layer member (air pole is used) of the embodiment of the invention 3.
Figure 17 is the example according to the stack fuel cell of the embodiment of the invention 3, be illustrated among Figure 15 along the supply of fuel of III-III line and the sectional view of emission path.
Figure 18 is the example according to the stack fuel cell of the embodiment of the invention 3, is the sectional view along the IV-IV line that is illustrated among Figure 16.
Figure 19 is the plane graph of the oxygen supply face side of the expression gas diffusion layer member relevant with first execution mode in the embodiment of the invention 4.
Figure 20 is in Figure 19, along the cross section target view of a-a line.
Figure 21 is the plane graph of the supply of fuel face side of expression gas diffusion layer member shown in Figure 19.
Figure 22 is that expression utilizes gas diffusion layer member shown in Figure 19 and constitutes the plane graph of oxygen supply face side of the main portion of polymer electrolyte fuel cell of air pole.
Figure 23 is in Figure 22, along the cross section target view of i-i line.
Figure 24 is the plane graph of the oxygen supply face side of the expression gas diffusion layer member relevant with second execution mode in the embodiment of the invention 4.
Figure 25 is in Figure 24, along the cross section target view of b-b line.
Figure 26 is the plane graph of the supply of fuel face side of expression gas diffusion layer member shown in Figure 24.
Figure 27 is the plane graph of the oxygen supply face side of the expression gas diffusion layer member relevant with the 3rd execution mode in the embodiment of the invention 4.
Figure 28 is in Figure 27, along the cross section target view of c-c line.
Figure 29 is the plane graph of the supply of fuel face side of expression gas diffusion layer member shown in Figure 27.
Figure 30 is that the ideograph of the reaction-injection moulding of gas diffusion layer member shown in Figure 19 with main cross section of mould made in expression.
Figure 31 is the oblique view that is illustrated in the gas diffusion layer member of another execution mode in the embodiment of the invention 4.
Figure 32 is plane graph and the sectional view with the gas diffusion layer member of the polymer electrolyte fuel cell shown in first execution mode of the embodiment of the invention 5.
Figure 33 is the amplification view of collector body shown in Figure 32.
Figure 34 is an execution mode that utilizes the polymer electrolyte fuel cell of gas diffusion layer member shown in Figure 32.
Figure 35 is the schematic diagram of expression with first operation of gas diffusion layer member when embedding shaping of the polymer electrolyte fuel cell shown in first execution mode of the embodiment of the invention 5.
Figure 36 is the schematic diagram of expression with second operation of gas diffusion layer member when embedding shaping of the polymer electrolyte fuel cell shown in first execution mode of the embodiment of the invention 5.
Figure 37 is the sectional view with the gas diffusion layer member of the polymer electrolyte fuel cell shown in second execution mode of the embodiment of the invention 5.
Figure 38 is that expression is in the manufacture method with the gas diffusion layer member shown in first execution mode of embodiments of the invention 5 ideograph of an example of filling paste in the collector body mesh.
Figure 39 is illustrated in in the gas diffusion layer member manufacture method shown in first execution mode of embodiments of the invention 5 ideograph of the example when burning till foaming body.
Figure 40 is the sectional view of main portion of the fuel cell of the expression embodiment of the invention 6.
Figure 41 is in Figure 40, along the target view of II-II line, is the plane graph of the expression gas diffusion layer member relevant with the present invention.
Figure 42 is in Figure 40, along the target view of III-III line, is the plane graph of the expression gas diffusion layer member relevant with the present invention.
Figure 43 is in Figure 40, along the target view of IV-IV line, is the plane graph of the expression gas diffusion layer member relevant with the present invention.
Figure 44 is that expression is used in manufacturing with the ideograph of Figure 41 to an example of the device of the conductivity porous body of gas diffusion layer member shown in Figure 43.
Figure 45 is the plane graph that expression is used in the dividing plate of the gas diffusion layer member relevant with another execution mode of the embodiment of the invention 6.
Figure 46 is the oblique view of an execution mode of the cell member in the expression embodiment of the invention 7.
Figure 47 is the oblique view that expression utilizes the fuel cell of cell member shown in Figure 46.
Figure 48 is the oblique view of one of expression terminal shape example.
Figure 49 is the oblique view of one of expression terminal shape example.
Figure 50 is the oblique view of one of expression terminal shape example.
Figure 51 is the oblique view of one of expression terminal shape example.
Figure 52 is the oblique view of one of expression terminal shape example.
Figure 53 is the oblique view of one of expression terminal shape example.
Figure 54 is the oblique view of another execution mode of the expression cell member relevant with the embodiment of the invention 7.
Figure 55 is the oblique view of another execution mode of the expression cell member relevant with the embodiment of the invention 7.
Figure 56 is expression when making cell member, at the sectional view of the operation of conductivity porous body painting catalyst layer.
Figure 57 is that expression is with the sectional view of conductivity porous body by the state of formalizing shape cut-out.
Figure 58 is the sectional view that is illustrated in the state of conductivity porous body mounting terminal.
Figure 59 is illustrated in the sectional view of arranging the state of dielectric substrate between the conductivity porous body.
Figure 60 is the ideograph that the reaction-injection moulding mould of cell member is made in expression.
Figure 61 is expression when making cell member, cuts off conductivity porous matter thin slice and the sectional view of the operation of painting catalyst layer.
Figure 62 is expression is formed the state of film-electrode bond by conductivity porous body and dielectric substrate a sectional view.
Figure 63 is the side view of other execution modes of the expression cell member relevant with the embodiment of the invention 7.
Figure 64 is the schematic diagram to the main portion of the polymer electrolyte fuel cell of the face direction fuel arranged supply department of cell member of the expression embodiment of the invention 7.
Figure 65 is in Figure 64, along the cross section target view of a-a line.
Figure 66 is the schematic diagram to the main portion of the polymer electrolyte fuel cell of the face direction fuel arranged supply department of cell member of the expression embodiment of the invention 7.
Figure 67 is the schematic diagram to the main portion of the polymer electrolyte fuel cell of the face direction fuel arranged supply department of cell member of the expression embodiment of the invention 7.
Figure 68 is the partial cross section figure to the main portion of the polymer electrolyte fuel cell of the face direction fuel arranged supply department of cell member of the expression embodiment of the invention 7.
Embodiment
At first explanation is used for conductivity porous body of the present invention and resin portion below.
Be used for conductivity porous body of the present invention, can select carbon system porous bodies such as carbon paper, carbon cloth for use, but select for use gas diffusibility and conductivity all good, have the metal of three dimensional network ocular structure and be advisable, as the thin slice of sintering metal powder, metal nonwoven fabrics, folded net etc.Wherein,, can suitably regulate the porosity or thickness as the conductivity porous body of above-mentioned gas diffusion layer member, and the thin slice of the more rich metal dust of the available metal species of sintering, use preferably.And, in metal dust, add behind adhesive, the solvent mixingly, and the doping blowing agent becomes the foaminess slurry, then, carries out sintering behind the foaming and molding, it is higher that getable thus foaming metal sintering thin slice can produce the porosity, therefore more suitable.
And, be used in resin portion of the present invention, for example have, thermoplastic resin, thermosetting resin or elastomer (elastomer), can according to composite porous body 10 ' purposes suitably select.
Have as thermoplastic resin: polyethylene, polystyrene, the AS resin, ABS resin, polypropylene, vinyl chloride resin, isobutylene resin, the plastics of general usefulness such as polyethylene terephthalate, perhaps, polyamide, Merlon, polyacetals, sex change polyhenylene ether, the general engineering plastics of using such as polybutylene terephthalate, perhaps, poly-p-phenylene sulfide, polyarylate, polysulfones, polyether sulfone, polyether etherketone, Polyetherimide, polyamidoimide, liquid crystal polymer, polyimides, superelevation engineering plastics such as polyphthalamide, perhaps, fluororesin, ultra-high molecular weight polyethylene, thermoplastic elastomer, polymethylpentene, give birth to the decomposability plastics, polyacrylonitrile, other resins such as cellulose-based plastics.
Have as thermosetting resin: phenolic resin, urea resin, Melantine, epoxy resin, unsaturated polyester resin, polyurethane, diallyl phthalate resin, silicones, alkyd resins etc.Have as elastomer: natural rubber, isoprene rubber, butadiene rubber, butyl rubber, ethylene propylene rubber, ethylene-vinyl acetate copolymer, chloroprene rubber, chlorosulfonated polyethylene etc.
Below, describe embodiments of the invention in detail.
Composite porous body 10 of the present invention ', as shown in Figure 1, by laminar conductivity porous body 11 Hes, the rectangular thin plate shape that the resin portion 12 that prolongs to the face direction of this conductivity porous body 11 forms as one constitutes.
Conductivity porous body 11 is the rectangular thin plates with three dimensional network ocular structure, and is communicated in all directions at the pore of the opening of sidepiece, and has gas permeability and water absorption, also has characteristics such as light weight, surface area be big.And this conductivity porous body 11 is, metallic might as well, crystallinity graphite or contain noncrystalline amorphous carbon carbon element matter might as well, and the metal nonwoven fabrics might as well.
12 one-tenth of resin portion are connected in the lamellar of periphery outside the conductivity porous body 11, to form with the conductivity porous body 11 roughly the same thickness sections of nothing differences.And this resin portion 12 contains not shown inorganic filler.This inorganic filler becomes the fibrous while, and in resin portion 12, contain more than the 5wt%, below the 60wt%.At this, the above-mentioned fibrous aspect ratio of representing is more than 5.In the present embodiment, the external diameter of inorganic filler is more than the 3.5nm, below the 30 μ m, is more preferred from more than the 3.5nm, below the 10 μ m.And, resin portion 12, as shown in Figure 1, can be for smooth, but with the screw inserting hole with the hole, equipment is chimeric is provided with also passable when embedding described later is shaped with groove shape, the rib shape that improves intensity, lug boss etc.
By these conductivity porous bodies 11 and resin portion 12 form as one and the composite porous body 10 that constitutes ', constitute a thin-plate element on the whole, and resin portion 12 is that fixing or clamping etc. are installed on above-mentioned various device, is utilized with filter, suction member, radiator etc.
The manufacture method of metal conductivity porous body 11 then, is described.Above-mentioned conductivity porous body 11 can be made by the whole bag of tricks, for example, can will comprise the slurry S of metal dust with thin shape dry green list (green sheet) G that is shaped, burn till and make.
Fig. 2 is that expression constitutes by the summary that scraping blade (doctor blade) method is configured as slurry S green single manufacturing installation 80 of thin shape.
Slurry S is, for example (for example with metal dusts such as SUS316L, organic bond, methylcellulose or hydroxypropyl methylcellulose), solvent (water) mixes, at this, add as required, the blowing agent that distils or vaporize by heat treated (for example, carbon number be 5～8 water-insoluble hydrocarbon be organic solvent (for example, neopentane, hexane, heptane)) or defoamer (ethanol) etc.
Be green single manufacturing installation 80, at first, the feeding funnel 81 of slurry S arranged, supplies slurry S on by the carrying thin slice 82 of roller 83 conveyances from storage.The slurry S of carrying on the thin slice 82 prolongs between carrying thin slice 82 that moves and scraping blade 84 and is shaped with required thickness.
The slurry S that is shaped, by 82 conveyances of carrying thin slice, and by heating furnace 86.Then, along with dry in heating furnace 86, form the green single G of SUS316L powder by the state of organic bond joint.In addition, if among the slurry S when including blowing agent, will carrying thin slice 82 on slurry S under the prolongation state, before the dried, under the high humility atmospheric condition, carry out heat treated, and by blowing agent is foamed, after making it become the foaming slurry, carry out dried again, and form green single G.
This green single G, after separating from carrying thin slice 82, in not shown vacuum furnace by degreasing, burn till, organic bond is removed therefrom, and becomes the conductivity porous body 11 of each metal dust phase sintering.
Then,, resin portion 12 is set along its whole edge according to Fig. 3 explanation outer peripheral edges portion at conductivity porous body 11, and make composite porous body shown in Figure 1 10 ' one of a method execution mode.
In the die cavity 72 of 70,71 formation of a pair of mould, arrange conductivity porous body 11 with built in items, and will be filled in the die cavity 72 from running channel 73 by the molten resin 75 that cast gate 74 sprays, thereby the composite porous body 10 that formation is become one by conductivity porous body 11 and resin portion 12 '.At this, the molten resin 75 that sprays in die cavity 72 contains not shown inorganic filler.This inorganic filler when becoming fibrous (aspect ratio is more than 5), contains more than the promising 5wt%, below the 60wt% in molten resin 75.And the external diameter of inorganic filler is more than the 3.5nm, below the 30 μ m, is more preferred from more than the 3.5nm, below the 10 μ m.Therefore, evenly be dispersed with inorganic filler in the molten resin 75, and seek the homogenization of the flowability of this resin 75, simultaneously, when above-mentioned injection, inorganic filler is wrapped in the mesh of the pore of the outer peripheral edges opening that is divided in conductivity porous body 11, thereby in the outer peripheral edges of conductivity porous body 11, the aperture area of this pore dwindles.And, under this state, molten resin 75 sclerosis, and the outer peripheral edges portion of conductivity porous body 11 and resin portion 12 engage.
In addition, by embed to be shaped forming 10 ' time of composite porous body, if the thickness of die cavity 72 when making matched moulds (mould opens and closes the size of direction), less than conductivity porous body 11, and during matched moulds on 70,71 on mould, make 11 compressions 3～90% of conductivity porous body, even then the injection of molten resin 75 is pressed when acting on conductivity porous body 11, the die cavity 72 interior occurrence positions that also can be suppressed at conductivity porous body 11 depart from, simultaneously, also can improve the surface smoothness of conductivity porous body 11, can adjust the hole diameter and the porosity of conductivity porous body 11.
And, the hole diameter of this adjusted conductivity porous body 11 and the porosity and, addition in the size of inorganic filler and the molten resin 75 (resin portion 12), the decision that each is relative, that is, when above-mentioned injection, as mentioned above, inorganic filler be wrapped in the outer peripheral edges opening that is divided in conductivity porous body 11 pore mesh and determine dwindle the aperture area of this pore so that make in outer peripheral edges.For example, the hole diameter of conductivity porous body 11 be 10 μ m above, below the 2mm, and the porosity is more than 40%, 98% when following, make inorganic filler keep above-mentioned size and content to get final product.
At this, for example have as above-mentioned inorganic filler, fibrous materials such as glass fibre, carbon fibre, carbon nanotube or broken-staple metal fibre, perhaps, metal oxides such as aluminium oxide, zirconia, zinc oxide, potassium titanate, aluminium borate, perhaps, non-oxide ceramics acicular crystals such as carborundum, aluminium nitride (what is called, whisker) material etc.
As mentioned above, according to the composite porous body 10 of present embodiment ', owing to be provided with resin portion 12, thereby can improve the rigidity of conductivity porous body 11, and can seek the raising of its operability.And, because resin portion 12 prolongs to the face direction just as outstanding from the outer peripheral edges of conductivity porous body 11, therefore, will composite porous body 10 ' in wear the device erection opening part can be defined as this resin portion 12, thereby can be easily, wear device with high accuracy and use the hole, simultaneously, also can control the minimizing of effective usable floor area of conductivity porous body 11 to greatest extent.Especially, because resin portion 12 contains inorganic filler, therefore can seek the high strength of resin portion 12 itself, its result can realize the high strength of composite porous body 10 ' integral body, and can improve its operability more.
And, according to the composite porous body 10 of present embodiment ' manufacture method since by embed be shaped form composite porous body 10 ', when therefore can form resin portion 12 with high accuracy, can form easily this composite porous body 10 '.And, because resin portion 12 contains inorganic filler, therefore embed when being shaped, even molten resin 75 desires are from the pore to the outer peripheral edges opening of conductivity porous body 11, when flowing in the inside of this conductivity porous body 11, also because of inorganic filler is wound in the mesh of dividing this pore, thereby in the outer peripheral edges of conductivity porous body 11, the aperture area of this pore dwindles.Therefore, when above-mentioned embedding is shaped, the inside that molten resin 75 unrestrictedly flows in conductivity porous body 11 can be suppressed, and the minimizing (suppressing the effect that effective usable floor area reduces) of effective usable floor area of conductivity porous body 11 can be controlled to greatest extent.In addition, as mentioned above, when above-mentioned embedding is shaped, because inorganic filler is wound in the pore mesh of the outer peripheral edges opening that is divided in conductivity porous body 11, therefore hardened with molten resin 75 under this state, even and control the inside that molten resin 75 flows in conductivity porous body 11 to greatest extent, also realize the firm joint (improving the bond strength effect) of resin portion 12 and conductivity porous body 11.
And represented in the above-described embodiment all shapes of each member or compound mode etc. are an example just, and in not breaking away from the scope of purport of the present invention, can carry out various changes according to designing requirement.For example, in the above-described embodiment, though be provided with resin portion 12 at the whole edge of the outer peripheral edges of conductivity porous body 11, can conductivity porous body 11 decide the peripheral direction position, the resin portion of institute's measured length is set.
In above-mentioned action effect, carried out demonstration test about the effect (hereinafter to be referred as " effect 1 ") of the effective usable floor area minimizing of above-mentioned inhibition and the effect (hereinafter to be referred as " effect 2 ") of above-mentioned raising bond strength.As the composite porous body that is provided in this test, embodiment is divided into two kinds, they be all by porous body and resin portion with similar thickness, do not have the section difference, the thickness composite porous body of 0.2mm slightly, form by above-mentioned embedding.Results such as filling kind that Fig. 4 listed the molding condition that comprises when embed being shaped, contain in resin portion 12 and filler external diameter.In this chart, effect 1 listed numeric representation composite porous body flows in the degree of depth of resin portion from outer peripheral edges.And the loading of filler be about 40%wt at embodiment and comparative example, and resin portion is formed by syndiotactic polystyrene.According to this figure, when visible inorganic filler was fibrous, effect was better.And, though when containing inorganic filler, then effect 1,2 just improves, and when not containing inorganic filler, also has effect 1,2.
Illustrate composite porous body 10 ' the application example.
Fig. 5 represents, is applied to the composite porous body of the gas diffusion layer member 10 of polymer electrolyte fuel cell.The structure of this gas diffusion layer member 10 is that a plurality of conductivity porous bodies 11 when filling the gap between each conductivity porous body 11, just as surrounding whole periphery, are provided with resin portion 12 under the state that the face direction is arranged at certain intervals.In addition, be connected with at an end of each conductivity porous body 11, the terminal that extends to resin portion 12 peripheries is with joint 2.Terminal is deposited in each the conductivity porous body 11 that embeds before being shaped with joint 2, and is shaped by embedding, and becomes one with resin portion 12.
Moreover, should though be provided with terminal with joint 2,, the situation of terminal with joint 2 that be not provided with arranged also with in the example as the gas diffusion layer member of polymer electrolyte fuel cell at conductivity porous body 11.That is, in the stack fuel cell with the structure of cell cells overlap, arrange dividing plate between the cell unit with conductivity.Thereby, even if terminal joint 2 is not set in conductivity porous body 11, also can the cell unit is connected in series.Also have the plane battery unit member 10 as shown in Figure 54 and Figure 55 ", at conductivity porous body 11 direct connecting wirings, so terminal joint 2 need not be set.At this moment, can adopt following connecting elements: with each conductivity porous body 11 with X-shaped shape interconnective " コ " word shape conductivity connecting elements 18 (Figure 54); Or have, insert near resin frame 13 parts two pairs of conductivity porous bodies 11 of adjacent two couple clamping part 19a and, conductivity clip 19 (Figure 55) connecting elements of the connecting portion 19b that prolongs to conductivity porous body 11 from this clamping part 19a.
And, this composite porous body 10 ' the application example, have more than the gas diffusion layer member that is limited to polymer electrolyte fuel cell.Also can be as the fin of filler supporting plate, the suction member that is used for humidifier, cooling computer CPU etc. in the filter of air purifier, the packed tower etc.
Fig. 5 represents, the gas diffusion layer member 10 relevant with embodiment among the present invention 2.This gas diffusion layer member 10 constitutes: be provided with laminar conductivity porous body 11; From the outstanding terminal of conductivity porous body 11 with joint 2; Surround conductivity porous body 11 around and terminal is exposed to the resin frame 13 of resin frame 13 outside 13a with the front end 2a of joint 2.
This gas diffusion layer member 10, for the electronics that makes current collection in the conductivity porous body 11 is flowed out with joint 2 by terminal or for making the electron stream that is flowed into joint 2 by terminal among the conductivity porous body 11, conductivity porous body 11 and terminal should be formed by high conductive material with joint 2.In addition, if corrosion phenomenon is when being a problem, utilize corrosion resistance material such as stainless steel to be advisable.
In the execution mode of gas diffusion layer member 10 shown in Figure 5, be respectively arranged with terminal joint 2 at each conductivity porous body 11, but, when if the conductivity of conductivity porous body 11 is low, for preventing that current collection power from reducing, can adopt following construction of condition: as shown in Figure 6, make each terminal outstanding from the two ends of conductivity porous body 11 with joint 2; As shown in Figure 7, increase conductivity porous body 11 and the contact area of terminal with joint 2; Or as shown in Figure 8, make terminal with the shape of joint 2, prolong and just as respectively formation such as outstanding to the length direction of conductivity porous body 11 from two ends.
In addition, terminal exposes at any one positions such as the side of resin frame 13 13a, surface (above and below) 13b, 13c with joint 2 and gets final product.For example, integral body is embedded under the state of resin frame 13, has the formation (Fig. 9) that terminal exposes with the front end 2a of joint 2 only; Perhaps, any one is showed out at above and below 13b, 13c, and the formation of then not exposing at side 13a (Figure 10) is also passable.And, as shown in figure 11, can adopt, whole terminal is imbedded in the resin frame 13 with joint 2, whole terminal is set connects the through hole h of resin frame 13 with joint 2, and the formation that terminal exposes at the inner peripheral surface of this through hole h with joint 2.
Conductivity porous body 11, in polymer electrolyte fuel cell, because of it has gas permeability and conductivity by the three dimensional network ocular structure, become the sheet-like member of hold concurrently gas diffusion layers and collector plate thus, particularly, for example it is the institute's shape of being wanted formation such as the thin slice, foaming metal sintering thin slice, metal nonwoven fabrics with sintering metal powder, folded net.
At this, an example as conductivity porous body 11 is described---with metal powder sintered porous matter foaming metal sintering thin slice 11 (the conductivity porous bodies of making 11).This foaming metal sintering thin slice 11 for example, is configured as dry green single manufacturing the behind the thin shape by burning till the slurry S that will comprise metal dust.
Slurry S is, for example, with metal dusts such as SUS316L, organic bond (for example, methylcellulose or hydroxypropyl methylcellulose), solvent (water) mixes, at this, add as required, (for example by the blowing agent of heat treated distillation or vaporization, carbon number be 5～8 water-insoluble hydrocarbon be organic solvent (for example, neopentane, hexane, heptane)), defoamer (ethanol) etc.Will be by the scraping blade method, being shaped makes slurry S for thin green single manufacturing installation 80, represents on Figure 12.
In green single manufacturing installation 80, at first, the feeding funnel 81 of slurry S is arranged, supplies slurry S on by the carrying thin slice 82 of roller 83 conveyances from storage.The slurry S of carrying on the thin slice 82 prolongs between carrying thin slice 82 that moves and scraping blade 84 and is shaped with required thickness.
The slurry S that is shaped is passed through successively by carrying thin slice 82 conveyances, carries out the foaming groove 85 and the heating furnace 86 of heat treated.In foaming groove 85,, therefore can slurry S not cracked, and make the blowing agent foaming owing to be under high humility atmosphere, to carry out heat treated.And,, between particle, form the green single G of the metal dust in cavity by the state of organic bond joint if, then form because of foaming forms empty slurry S drying in heating furnace 86.
Should green single G, after separating from carrying thin slice 82, in not shown vacuum furnace, carry out degreasing, burn till, remove organic bond thus, can obtain the conductivity porous body of the mutual sintering of each metal dust.This conductivity porous body by suitably size cut-out, be can be used as foaming metal sintering thin slice 11.
The foaming metal sintering thin slice 11 of Xing Chenging is connected with terminal joint 2 as mentioned above.Terminal is made of no gas permeability, high conductive sheet metal or electroconductive resin with joint 2, and is provided with just as outstanding from conductivity porous body 11.
Terminal in the present embodiment is made of sheet metal with joint 2, from conductivity porous body 11 to the face direction just as outstanding, with to the superimposed state of conductivity porous body 11 parts, weld by modes such as spot welding.
The then manufacture method of the relevant gas diffusion layer member 10 of explanation and the embodiment of the invention 2.Its method is that foaming metal sintering thin slice 11 is embedded shaping as built in items.For a gas diffusion layer member 10, embed 4 foaming metal sintering thin slices 11 here.
At first, as shown in figure 13, earlier terminal is welded in each foaming metal sintering thin slice 11 with joint 2, it is become one, again these are welded with 4 the foaming metal sintering thin slices 11 of terminal, in the face direction is arranged in reaction-injection moulding shown in Figure 14 die cavity 72 with formation between a pair of mould 70,71 of mould at certain intervals with joint 2.
In die cavity 72, by protruding in pin members 76 in the die cavity 72 when pressing each terminal with joint 2, rely on each each foaming metal sintering thin slice 11 of mould 70,71 clampings, by the pressure fixing foaming metal sintering thin slice 11 and the terminal joint 2 of the resin that sprays, so that it is not removable in die cavity 72.Therefore, owing to, therefore, the two sides 11a of foaming metal sintering thin slice 11, the major part of 11b can be exposed to the surface of gas diffusion layer member 10 to fill molten resin with foaming metal sintering thin slice 11 thickness much at one.
And, if die cavity 72 thickness are slightly less than foaming metal sintering thin slice 11 when making mold closing, and during mold closing between mould 70,71, make 11 compressions 3～90% of foaming metal sintering thin slice, then press with respect to sprayed resin, when foaming metal sintering thin slice 11 can be fixed in the die cavity 72, also can improve the evenness of foaming metal sintering thin slice 11.
And, in the die cavity 72 of mold closing, fill the molten resin 75 that sprays by running channel 73 by cast gate 74, thus around each foaming metal sintering thin slice 11, integrally formed and the identical resin frame 13 of foaming metal sintering thin slice 11 thickness.
At this moment, because two sides 11a, the 11b of foaming metal sintering thin slice 11 link to each other with mould 70,71, so resin do not cover whole 11a, 11b, and face 11a, the 11b of foaming metal sintering thin slice 11 expose from resin frame 13.And, in the pore of the sidepiece 11c of foaming metal sintering thin slice 11 opening, molten resin infiltrates thickness and reaches about 5 μ m～1000 μ m and harden, therefore can be with foaming metal sintering thin slice 11 and resin frame 13 firm joints, and the sidepiece 11c of whole foaming metal sintering thin slice 11 is covered by resin frame 13.
At this, with respect to resin frame 13 outsides (side) 13a that is shaped, terminal is with joint 2, need not its front end 2a unanimity, and outstanding also harmless.And, because molten resin even cover the front end 2a of terminal, when front end 2a is not exposed to the outside 13a of resin frame 13,, front end 2a is exposed gets final product by grind resin frame 13 etc. with joint 2.
And if the hole diameter or the porosity of foaming metal sintering thin slice 11 are too small, then molten resin can not infiltrate in the pore, thereby air seal effect and grappling effect might become insufficient.In addition, if the hole diameter or the porosity are excessive,, can't bear that ester moulding is pressed and the compression during hardening of resin causes the possibility of being out of shape and have then because insufficient strength.Therefore, foaming metal sintering thin slice 11, hole diameter are about 10 μ m～2mm, the porosity is about 40～98%, are advisable.
And, the material of resin frame 13, can select thermoplastic resin, elastomer (containing rubber) for use but etc. the material of reaction-injection moulding, and do not have conductivity and gas permeability is advisable, this can suitably be selected to get final product after taking into full account heat resisting temperature or hardness etc.For example, if select soft resin for use, then can improve the sealing of conductivity porous body 11 sidepiece 11c.
In the above-described embodiment, adopted when forming terminal, sheet metal has been welded in method on the conductivity porous body 11 with joint 2.To this, also can adopt the manufacture method of the following gas diffusion layer member 10 relevant with other execution modes of the present invention.
Promptly, only conductivity porous body 11 as built in items, form resin frame 13 by embedding, formation on resin frame 13 then, the wiring that prolongs and be exposed to resin frame 13 outside 13a from face 11a, 11b by plating, evaporation, spraying plating etc., and its as terminal with joint 2.Can suppress the distortion of conductivity porous body 11.And,, therefore reliably easily make front end 2a be exposed to outside 13a owing to form terminal with joint 2 on the surface of resin frame 13.
In addition, another execution mode as the manufacture method of gas diffusion layer member 10 can adopt, by double-colored forming technique, the reaction-injection moulding electroconductive resin, and form terminal joint 2, thereby the reaction-injection moulding non-conductive resin forms the method for resin frame 13 thus.
The gas diffusion layer member 10 that produces according to above-mentioned manufacture method, form catalyst layer and as air pole or fuel electrodes at face of each foaming metal sintering thin slice 11, between it, clamp dielectric substrate, connect each terminal joint 2 successively, can constitute the plane battery unit of polymer electrolyte fuel cell thus.
Gas diffusion layer member of the present invention applicable to, shown in Figure 64 to Figure 68, to the polymer electrolyte fuel cell of the structure of the face direction fuel arranged supply department 30 of gas diffusion layer member.
At this moment, shown in Figure 64, its structure is, has foaming metal sintering thin slice (conductivity porous body) 112 Hes of the gas diffusion layer member 110 of fuel electrodes A, and the porous matter portion 31 of fuel supplies 30 is directly contact.Therefore, as Figure 65 (in Figure 64, cross section target view along the a-a line) shown in, because the intercommunicating pore 113a to the face direction perforation of resin frame 113 is set, and, porous matter portion 31 and foaming metal sintering thin slice 112 are communicated with by this intercommunicating pore 113a, simultaneously, secondary product in the time of can discharging generating, i.e. carbon dioxide gas.
In addition, by install covering the tabular component 115 on foaming metal sintering thin slice 112 surfaces, and clog and fuel supplies 30 and resin portion 32 between the gap, thereby can prevent the fuel leak phenomenon that takes place by foaming metal sintering thin slice 112.Therefore, for example, can realize, above-mentioned tabular component 115 sides are arranged in the back side of LCD and are applicable to the structure of ultrathin notebook PC.
In addition, as the structure of connected porous matter portion 31 and foaming metal sintering thin slice 112, shown in Figure 66, it is also passable that the groove 113a that prolongs to the face direction is set on the surface of resin frame 113.At this moment, if also gas diffusion layer member 110 side surfaces at tabular component 115 form the groove 115a that prolongs to the face direction, make this groove 115a be communicated in the groove 113a and foaming metal sintering thin slice 112 surfaces of resin frame 113, then, can pass through this groove 115a, than foaming metal sintering thin slice 112 effective supply fuel more, the discharging carbon dioxide gas.
And, shown in Figure 67 and Figure 68, if gas diffusion layer member 110 sides with air pole B, arrange as when covering tabular component 116 members such as grade on foaming metal sintering thin slice (conductivity porous body) 112 surfaces, for with air supply in foaming metal sintering thin slice 112, can design following structure:, form the groove 116a (Figure 67) that is communicated in foaming metal sintering thin slice 112 on tabular component 116 surfaces; Or, form groove 213a (Figure 68) etc. on resin frame 213 surfaces of gas diffusion layer member 210.
According to the gas diffusion layer member the 10, the 20th of embodiments of the invention 3,, shown in Figure 15 and 16, gas- diffusion electrode 11,21 and that each is made of laminar conductivity porous body, cover this gas-diffusion electrode (conductivity porous body) 11,21 around and the resin portion 12,22 that prolongs to the face direction, the rectangular thin plate shape that forms as one.
Cross section with polymer electrolyte fuel cell of the present invention 100 main portions of this gas diffusion layer member 10,20, expression on Figure 17 and 18.
This polymer electrolyte fuel cell 100, adopted so-called stack to constitute, that is, the cell unit 130 that will constitute by gas diffusion layer member 10,20 and dielectric substrate 121, the mode of clamping dividing plate 122,123,124 back multiple-level stacks therebetween.And, Figure 17 is according to the cross section target view along the III-III line with the part of gas diffusion layer member 10 expression at Figure 15, Figure 18 is according to the cross section target view along the IV-IV line with the part of gas diffusion layer member 20 expression at Figure 16, and is the schematic diagram of representing fuel cell 100 with different cross section.
Gas- diffusion electrode 11,21, the rectangular thin plate that the conductivity porous body with three dimensional network ocular structure of serving as reasons constitutes, and owing to be communicated with all directions at the pore of surface opening is so have gas permeability, also have characteristics light, that surface area is big.
Cover the resin portion 12,22 that is provided with around this gas- diffusion electrode 11,21 for lamellar, and be connected in the outer peripheral edges of gas- diffusion electrode 11,21, with gas- diffusion electrode portion 11,21 roughly the same thickness, do not have the section difference and form.
And the gas diffusion layer member 10,20 that these gas- diffusion electrodes 11,21 and resin portion 12,22 form as one constitutes a thin-plate element on the whole.
In the fuel cell shown in Figure 17 and 18, the gas-diffusion electrode 11 of gas diffusion layer member 10 is the fuel electrodes by fuel feed passage 101 fuel supplying.On the other hand, the gas-diffusion electrode 21 of gas diffusion layer member 20 is the air pole by oxygen supply path 10 3 supply air.Below, the gas-diffusion electrode of fuel electrodes is called the fuel diffusion electrode, and the gas-diffusion electrode of air pole is called the oxygen diffusion electrode.
As shown in figure 15, gas diffusion layer member 10, be provided with: be connected in fuel diffusion electrode 11 and the supply of fuel that is communicated in its pore with through hole (first fluid service duct) 10a and fuel draining with through hole (first fluid discharge-channel) 10b, the air supply that is not connected in fuel diffusion electrode 11 and is arranged at a distance of the certain distance position discharges with through hole (second fluid drainage channel) 10d with through hole (the second fluid service duct) 10c and air, be arranged at four angles of resin portion 12 and insert the bolt insertion hole 10e of logical fixed-use bolt etc., and above-mentioned these holes all connect resin portion 12.
On the other hand, as shown in figure 16, gas diffusion layer member 20, be provided with: thus be connected in air supply through hole (the second fluid service duct) 20a and air discharging through hole (second fluid drainage channel) 20b that oxygen diffusion electrode 21 is communicated in its pore, be not connected in oxygen diffusion electrode 21 and be arranged at the supply of fuel of certain distance position apart through hole (first fluid service duct) 20c and fuel draining through hole (first fluid discharge-channel) 20d, be arranged at four angles of resin portion 22 and insert the bolt insertion hole 20e of logical fixed-use bolt etc., and above-mentioned these holes all connect resin portion 22.
These gas diffusion layer members 10,20 have same shape, and inside and outside difference is arranged, thereby can be used as fuel electrodes and air pole.That is, in gas diffusion layer member 10,20, be communicated in fuel diffusion electrode 11 and oxygen diffusion electrode 21 two through holes and, two through holes of Lian Tonging not, being separately positioned on straight line 101,201 is on the line symmetry of symmetry axis.In other words, because the supply of fuel discharging is symmetrically formed for straight line 101,201 with through hole with through hole and air supply discharging, therefore in two gas diffusion layer members that pile up, a side is turned over, and the through hole that is connected in the through hole of gas-diffusion electrode and is not connected in gas-diffusion electrode alternates, thereby, then can be communicated with each through hole if upturned two gas diffusion layer members of a side are piled up.
And,, be provided with the through hole that is communicated in gas diffusion layer member 10,20 each through hole and bolt insertion hole at the dielectric substrate 121 that is arranged between these gas diffusion layer members 10,20.That is, in dielectric substrate 121, be formed with: the supply of fuel through hole 121a that is communicated in gas diffusion layer member 10,20 through hole 10a, 20c; Be communicated in the air supply through hole 121b of through hole 10c, 20a; Be communicated in the fuel draining through hole 121c of through hole 10b, 20d; Be communicated in the air discharging through hole 121d of through hole 10d, 20b; And be communicated in the bolt insertion hole (not shown) of bolt insertion hole 10e, 20e.
In addition, be provided with the through hole that is communicated in each through hole of gas-diffusion electrode and bolt insertion hole at dividing plate 122.That is, in dividing plate 122, be formed with: the through hole 122a that is communicated in gas diffusion layer member 10,20 through hole 10a, 20c; Be communicated in the through hole 122b of through hole 10c, 20a; Be communicated in the through hole 122c of through hole 10b, 20d; Be communicated in the through hole 122d of through hole 10d, 20b; And be communicated in the bolt insertion hole (not shown) of bolt insertion hole 10e, 20e.
And, be used for sealing the barricade 123 on gas diffusion layer member 20 surfaces with air pole, be provided be communicated in be used for supply of fuel through hole 20c through hole 123a, be communicated in be used for the air discharging through hole 20b through hole 123b, be communicated in the bolt insertion hole (not shown) of bolt insertion hole 20e.
In addition, barricade 124 being used for sealing gas diffusion layer member 10 surfaces with fuel electrodes is formed with: be communicated in the through hole 10c that is used for supplying air through hole 124a, be communicated in be used for discharge fuel through hole 10b through hole 124b, be communicated in the bolt insertion hole (not shown) of bolt insertion hole 10e.
Gas diffusion layer member 10,20, dielectric substrate 121 and the dividing plate 122, the barricade 123,124 that pile up just as each through hole is communicated with, by insert logical bolt in bolt insertion hole after, nutted mode can be fixed as one.And the composition surface of resin portion 12,22 and dividing plate 122, resin portion 12,22 and dielectric substrate 121 etc. is by ultrasonic wave juncture fluid-tight engagement.And fuel diffusion electrode 11 and oxygen diffusion electrode 21 surface and dielectric substrates 121 are then by the hot pressing mode fluid-tight engagement.
By piling up above-mentioned gas diffusion layer member 10,20 and dielectric substrate 121, dividing plate 122,123,124, in fuel cell 100, form fuel-side service duct 101, fuel-side discharge-channel 102, oxygen side service duct 103 and oxygen discharge-channel 104.
Fuel-side service duct 101, be by with the through hole 123a of barricade 123, through hole 10a, the through hole 20c of each gas diffusion layer member 20, the through hole 121a of dielectric substrate 121 and the through hole 122a of dividing plate 122 of each gas diffusion layer member 10, be connected and form.
And fuel-side discharge-channel 102 is by through hole 10b, the through hole 20d of each gas diffusion layer member 20, the through hole 122c of dividing plate 122 and the through hole 124b of barricade 124 with each gas diffusion layer member 10, is connected and forms.
These fuel-side service ducts 101 and fuel-side discharge-channel 102 when being communicated in the fuel diffusion electrode (fuel electrodes) 11 of gas diffusion layer member 10, are not communicated in the oxygen diffusion electrode (air pole) 21 of gaseous diffusion with member 20.
And, oxygen side service duct 103, be by with the through hole 124a of barricade 124, through hole 10c, the through hole 20a of each gas diffusion layer member 20, the through hole 121b of dielectric substrate 121 and the through hole 122b of dividing plate 122 of each gas diffusion layer member 10, be connected and form.
And oxygen side discharge-channel 104 is by through hole 10d, the through hole 20b of each gas diffusion layer member 20, the through hole 122d of dividing plate 122 and the through hole 123b of barricade 123 with each gas diffusion layer member 10, is connected and forms.
These oxygen side service ducts 103 and oxygen side discharge-channel 104 when being communicated in the oxygen diffusion electrode (air pole) 21 of gas diffusion layer member 20, are not communicated in the fuel diffusion electrode (fuel electrodes) 11 of gas diffusion layer member 10.
Thereby, from the through hole 123a supplied fuel of barricade 123, be communicated with in the process of pore, to the interface of dielectric substrate 121 and catalyst layer C supply hydrogen by fuel diffusion electrode (fuel electrodes) 11.And ionization takes place by electrode reaction in this hydrogen on catalyst layer C, dielectric substrate 121 is moved to oxygen diffusion electrode (air pole) 21.Fuel after the electrode reaction is by fuel-side discharge-channel 102, from the through hole 124b of barricade 124 and the outside drain of fuel cell 100.
On the other hand, through hole 124a air supplied from barricade 124, in the process of passing through each oxygen diffusion electrode (air pole) 21 connection pore,, and together pass through oxygen side discharge-channel 104 with the water that reacts generation and discharge to the interface supply oxygen of dielectric substrate 121 and catalyst layer C.
And, arrive from fuel diffusion electrode (fuel electrodes) 11, dielectric substrate 121 is clamped and is arranged in the hydrogen of the oxygen diffusion electrode (air pole) 21 of opposite side, interface at dielectric substrate 121 and catalyst layer C, by with the airborne oxygen electrode reaction that is supplied in oxygen diffusion electrode 21, thereby water generation reaction.
On the other hand, the electronics by the ionization of hydrogen produces with being arranged at the loop (not shown) of gas diffusion layer member 10,20 outsides, moves to oxygen diffusion electrode (air pole) 21 from fuel diffusion electrode (fuel electrodes) 11.By this movement of electrons, can produce above-mentioned electric energy.
In addition, be used to form the conductivity porous body of gas- diffusion electrode 11,21, can select carbon system porous bodies such as carbon paper, carbon cloth for use, but, select for use gas diffusibility and conductivity all good and have the metal of three dimensional network ocular structure and be advisable, as the thin slice of sintering metal powder, metal nonwoven fabrics, folded net etc.Wherein,, can suitably regulate the porosity or thickness as the conductivity porous body of above-mentioned gas diffusion layer member, and the thin slice of the more rich metal dust of the available metal species of sintering, more suitable.
And, in metal dust, add behind adhesive, the solvent mixingly, the blowing agent that mixes again forms the foaminess slurry, and the foaming metal sintering thin slice that obtains with sintering behind the foaming and molding, can make the porous body of high porosity, therefore more is advisable.
In the present embodiment, the porosity or thickness can be suitably regulated in employing, the foaming metal sintering thin slice that available feed metal kind is also abundant.
At this,, the manufacture method of foaming metal sintering thin slice is described with reference to Figure 12.
Foaming metal sintering thin slice is to add behind adhesive, the solvent mixingly in metal dust, and the blowing agent that mixes is again made foaminess slurry S, and sintering obtains behind the foaming and molding.
Slurry S is, for example, with metal dusts such as SUS316L, organic bond (for example, methylcellulose or hydroxypropyl methylcellulose), solvent (water) mixes, at this, add as required, (for example by the blowing agent of heat treated distillation or vaporization, carbon number be 5～8 water-insoluble hydrocarbon be organic solvent (for example, neopentane, hexane, heptane)), defoamer (ethanol) etc.Represent among Figure 12, this slurry S by the scraping blade method, is configured as green single manufacturing installation 80 of thin shape.
In green single manufacturing installation 80, at first, the feeding funnel 81 of slurry S is arranged, supplies slurry S on carrying thin slice 83 from storage.Carrying thin slice 83 by roller 82 conveyances, and the slurry S of carrying on the thin slice 83, prolongs between carrying thin slice 83 that moves and scraping blade 84 and is shaped with required thickness.
The slurry S that is shaped, foaming groove 85 and the heating furnace 86 by carrying out heat treated successively by carrying thin slice 83 conveyances.In foaming groove 85, owing under high humility atmosphere, carry out heat treated, therefore can slurry S not cracked, make the blowing agent foaming.And, dry in heating furnace 86 as if the slurry S that forms the cavity because of foaming, then form and form the green single G of empty metal dust between particle by the state of organic bond joint.
Should green single G, after 82 separation of carrying thin slice, in not shown vacuum furnace, carry out degreasing, burn till, remove organic bond thus, can obtain the mutual sintering of each metal dust and become the foaming metal sintering thin slice (conductivity porous body) of three dimensional network ocular structure.
To cut off the conductivity porous body that forms as mentioned above by formalizing shape, embed shaping as built in items, and can produce, possess the gas- diffusion electrode 11,21 that constitutes by the conductivity porous body and the gas diffusion layer member 10,20 of resin portion 12,22 with one.
Promptly, shown in Figure 3, in the die cavity 72 that forms between a pair of mould 70,71, arrange the conductivity porous body as built in items, and will be from the molten resin 75 of running channel 73 by cast gate 74 injections, be filled in the die cavity 72, thereby form fuel diffusion electrode 11 (oxygen diffusion electrode 21) and resin portion 12 (resin portion 22) the all-in-one-piece gas diffusion layer member 10 (gas diffusion layer member 20) that constitutes by the conductivity porous body.Fuel diffusion electrode 11 and resin portion 12, molten resin are infiltrated to the degree of depth about 5 μ m～1000 μ m in the pore of fuel diffusion electrode 11 side mouth and are hardened firm thus joint.Connect each through hole of resin portion 12 (resin portion 22), during reaction-injection moulding, can form by mould.
For example, during with the material selection polypropylene of resin portion 12, with 180 ℃ of forming temperatures, 80kN matched moulds, be shaped and press 250kg/cm
2Reaction-injection moulding, and can obtain composite porous body 10 '.
In addition, formed gas diffusion layer member at 10,20 o'clock by embedding, die cavity 72 thickness when making mold closing (size of mould switch direction), a little littler than gas- diffusion electrode 11,21, and during mold closing between mould 70,71, make gas- diffusion electrode 11,21 compressions 3～90%, then can press by sprayed resin, gas- diffusion electrode 11,21 relative die cavitys 73 are fixed, simultaneously, also can be improved the evenness of gas- diffusion electrode 11,21.
In addition, if the hole diameter or the porosity of gas- diffusion electrode 11,21 is too small, then molten resin just can't infiltrate in the pore, thereby the grappling effect becomes inadequately, and can not fully obtain the bond strength with resin portion 12,22, phenomenon can occur peeling off at the junction surface.On the other hand, if the hole diameter or the porosity are excessive, then owing to insufficient strength, the compression stress in the time of can't bearing ester moulding pressure and hardening of resin finally causes distortion.Thereby hole diameter is about 10 μ m～2mm, the porosity is about 40～98%, is advisable.
On the other hand, the material of resin portion 12,22 can be selected thermoplastic resin, elastomer etc. for use, but to be the material of reaction-injection moulding get final product for it, can take into full account heat resisting temperature or hardness to this, suitably selects to get final product.
And, each member of formation shown in the above-described embodiment, its all shapes or combination etc. are examples, and in not breaking away from the scope of purport of the present invention, can carry out various changes according to designing requirement.
For example, in the above-described embodiment, be to be communicated with by the through hole that resin portion will be connected, form the service duct discharge-channel of fuel or air, but, can also adopt, form the groove shape that is communicated with resin portion outer rim and gas-diffusion electrode on the resin portion surface, and with this as service duct or discharge-channel, send constituting of air or fuel by pump pressure.
And, in the above-described embodiment, adopted the formation that catalyst layer C is formed in the gas-diffusion electrode surface coated, but can also adopt, for example, to in carbon paper (conductivity porous body), infiltrate catalyst pulp as catalyst layer, be arranged in the formation between dielectric substrate and the gas-diffusion electrode.At this moment, if constitute fuel cell, so that catalyst layer (carbon paper) is to the dielectric substrate hot press, and pressurization engages to gas-diffusion electrode (foaming metal sintering thin slice), and electronics or fluid (fuel or oxygen) are circulated freely.
From Figure 19 to Figure 21, represent the gas diffusion layer member 10 relevant with first execution mode of the embodiment of the invention 4.This gas diffusion layer member 10 has: laminar oxygen diffusion electrode 11; Be arranged at the resin portion 92 sidepiece 11c, that constitute by non-conductive material of this oxygen diffusion electrode (conductivity porous body) 11; Be arranged at the clathrate frame portion 93 of a side (oxygen supply face) the 11a side of oxygen diffusion electrode 11.
The oxygen diffusion electrode 11 that is provided with in the gas diffusion layer member 10 is formed by the conductivity porous material with three dimensional network ocular structure, and the one side is that oxygen supply face 11a, another side are electrode surface 11b.And, in the present embodiment, adopt as the conductivity porous material, can suitably regulate the porosity or thickness, and the also abundant foaming metal sintering thin slice of available feed metal.Foaming metal sintering thin slice adds behind adhesive, the solvent mixingly in metal dust, and forms the foaminess slurry at this doping blowing agent, sintering behind this slurry foaming and molding is obtained again.
That is, gas diffusion layer member 10 constitutes: the shielded while of its outer rim by resin portion 92, as shown in figure 19, oxygen supply face 11a side by clathrate frame portion 93 protected, in addition, as shown in figure 21, the all-round opening of electrode surface 11b side.
Figure 22 and 23 (in Figure 22) expression along the cross section target view that the i-i line is cut open, the main portion of the polymer electrolyte fuel cell of suitable this gas diffusion layer member 10.This fuel cell constitutes: air pole A and fuel electrodes B clamp dielectric substrate 121 layouts and have the fuel supplies 40 of preservation fuel supplying (nail alcohol solution here).Dielectric substrate 121 for example, is that polymer electrolytic film forms by fluororesin, and has in film that hydrogen ion is removable, but the character that does not allow electronics to pass through.
Air pole A forms the gas diffusion layer member 10 of present embodiment, and is arranged as electrode surface 11b towards dielectric substrate 121.Also be provided with catalyst layer C at electrode surface 11b, this catalyst layer C, coating comprises the polyelectrolyte solution that supports the atomic carbon particle of platinum series catalysts and forms.Electrode surface 11b of oxygen diffusion electrode 11 (catalyst layer C) and dielectric substrate 121 are fixed by the hot pressing fluid-tight engagement.And air pole A by the peristome 93a of clathrate frame portion 93, can be delivered to dielectric substrate 121 with the air (oxygen) that is supplied in oxygen diffusion electrode 11.
Fuel electrodes B forms with flat gas diffusion layer member 30.Gas diffusion layer member 30, oxygen diffusion electrode 11 with air pole A is the same, be made of foaming metal sintering thin slice, it constitutes: have, the fuel diffusion electrode of arranging with oxygen diffusion electrode 11 subtends 31, and cover the resin portion 32 of the sidepiece of this fuel diffusion electrode 31.Resin portion 32 by not having the resin of conductivity and gas permeability, forms as one with fuel diffusion electrode 31.
Gas diffusion layer member 30 makes fuel diffusion electrode 31 electrode surface 31b arrange towards dielectric substrate 121, and by the shut of arranging at its back side 33, whole supply of fuel face 31a is closed.Shut 33, the same with resin portion 32, also be to form, and at inner face 33a towards fuel diffusion electrode 31 by not having a resin of conductivity and gas permeability, and the supply of fuel face 31a of fuel diffusion electrode 31 between form the space and be provided with the supply of fuel groove 33b of circulation fuel.In addition, resin portion 32 is fixed by ultrasonic wave juncture fluid-tight engagement with shut 33.
Fuel supplies 40 is preserved fuel (nail alcoholic solution here), and it constitutes: the porous matter portion 41 by the felt of fuel diffusion electrode 31 fuel supplying in fuel electrodes B etc. constitutes is covered by resin frame 42.And, be stored in the fuel of porous matter portion 41, from being arranged at the fuel feed passage 42a of fuel supplies 40 resin frame 42,, finally can be supplied to fuel diffusion electrode 31 by supply of fuel groove 33b.The resin frame 42 of fuel supplies 40 and gas diffusion layer member 30, resin portion 32 and shut 33 are fixed by ultrasonic wave juncture fluid-tight engagement.
Be to have the fuel cell of said structure, the oxygen diffusion electrode 11 of air pole A and the fuel diffusion electrode 31 of fuel electrodes B have gas permeability and conductivity by the three dimensional network ocular structure, the member of so-called hold concurrently gas diffusion layers and collector plate.
In fuel cell, produce electric energy by following reaction.
That is, be supplied to hydrogen the fuel of fuel diffusion electrode 31 (fuel electrodes B), after by electrode reaction ionization taking place on the catalyst layer C, dielectric substrate 121 moved to oxygen diffusion electrode 11 (air pole A) from fuel supplies 40.And, hydrogen arrives in the oxygen diffusion electrode 11 (air pole A) of clamping dielectric substrate 121 and arranging at opposite side, at the interface of dielectric substrate 121 and catalyst layer C,, and generate water with the oxygen generating electrodes reaction from oxygen diffusion electrode 11 oxygen supply face 11a air supplied.
On the other hand, the electronics that is produced by the ionization of hydrogen the loop that is arranged at gas diffusion layer member 30 outsides (not shown), moves to air pole A (oxygen diffusion electrode 11) from fuel electrodes B (fuel diffusion electrode 31).By this movement of electrons, can produce electric energy.
And catalyst layer C is in the surface coated of oxygen diffusion electrode 11 and fuel diffusion electrode 31 and form, but, as long as, therefore, also can form on the surface of dielectric substrate 121 owing to be arranged at the interface of oxygen diffusion electrode 11 and fuel diffusion electrode 31 and dielectric substrate 121.
Below, on Figure 24-Figure 26, represent the gas diffusion layer member 50 relevant with second execution mode in the embodiment of the invention 4.This gas diffusion layer member 50 has: cut apart and be set to two laminar oxygen diffusion electrode 51,51; Respectively be arranged at the resin portion 52 sidepiece 51c, that constitute by non-conductive material of oxygen diffusion electrode 51; Be arranged at the clathrate frame portion 53 of a side (oxygen supply face) the 51a side of oxygen diffusion electrode 51; Connect the connecting portion 54 between each oxygen diffusion electrode 51,51.
The oxygen diffusion electrode 51 that is provided with at gas diffusion layer member 50, the same with oxygen diffusion electrode 11, formed by the conductivity porous material with three dimensional network ocular structure (foaming metal sintering thin slice), it simultaneously is oxygen supply face 51a, and another side then is electrode surface 51b.
Gas diffusion layer member 50 in the present embodiment, with gas diffusion layer member 10 differences in first execution mode, it constitutes, and cut apart to be set to two oxygen diffusion electrodes 51, and each oxygen diffusion electrode 51,51 is fixed with one by connecting portion 54 connections.Connecting portion 54, identical with resin portion 52 and clathrate frame portion 53, also be resin by non-conductive material, form as one with oxygen diffusion electrode 51 and resin portion 52.
That is, the gas diffusion layer member 50 of present embodiment constitutes: outer cause resin portion 52 is protected, and simultaneously as Figure 24 and shown in Figure 25, oxygen supply face 51a side is protected by grid frame portion 53, on the other hand, as shown in figure 26, the all-round opening of electrode surface 51b side.Be to constitute the polymer electrolyte fuel cell of air pole by this gas diffusion layer member 50, the gas diffusion layer member that also has two fuel diffusion electrodes in the fuel electrodes setting, can form thus, by this a pair of gas diffusion layer member to face direction two groups of cell unit side by side.
Between the series-connected cell unit, or the electrode of formation battery, also can terminal (not shown) be set at gas diffusion layer member.Terminal for example, is engaged in the conductivity porous body with belt metal foil by resistance welded etc. and can forms.
And, represent on Figure 27-Figure 29, with the gas diffusion layer member 60 that the 3rd execution mode is relevant in the embodiment of the invention 4.This gas diffusion layer member 60, the same with second execution mode, have: cut apart and be set to two laminar oxygen diffusion electrode 61,61; The resin portion 62 that constitutes by the non-conductive material of the both sides sidepiece 61c that is arranged at each oxygen diffusion electrode 61; Be arranged at the clathrate frame portion 63 of a side (oxygen supply face) the 61a side of oxygen diffusion electrode 61; Connect the connecting portion 64 between each oxygen diffusion electrode 60,60.
That is, the gas diffusion layer member 60 of present embodiment, by resin portion 62, the shielded while of both sides outer rim, remaining two side portions 61d, 61d are not provided with resin portion, and the end face of oxygen diffusion electrode 61 is being opened.And it constitutes, as Figure 27 and 28 (in Figure 27; along the cross section target view that the c-c line is cut open) shown in, oxygen supply face 61a side is by the 63 shielded whiles of clathrate frame portion, and 63a is opening by peristome; on the other hand, as Figure 28 and shown in Figure 29, electrode surface 61b all-round opening is being opened.Constituting in the polymer electrolyte fuel cell of air pole by this gas diffusion layer member 60, by also arrange gas diffusion layer member in fuel electrodes with two fuel diffusion electrodes, by this a pair of gas diffusion layer member, can form to face direction two groups of cell unit side by side.And the gas diffusion layer member 60 of present embodiment because the sidepiece 61d of oxygen diffusion electrode 61 is exposed to the outside, therefore can utilize this sidepiece 61d, is formed for connecting the wiring of each oxygen diffusion electrode 61.
At this, the manufacture method of the gas diffusion layer member 10 of the embodiment of the invention 4 will be described in conjunction with Figure 30.
Gas diffusion layer member 10, earlier with the conductivity porous body as built in items, embed shaping, again with this conductivity porous body as oxygen diffusion electrode 11, and form other parts (resin portion 92, clathrate frame portion 93), and be fabricated to one by sprayed resin.
Expression embeds molding die on Figure 30.Utilize this mould, in the die cavity 72 that between a pair of mould 70,71, forms, arrange conductivity porous body (oxygen diffusion electrode) 11 as built in items, in die cavity 72, fill from the molten resin 75 of running channel 73 again, form the gas diffusion layer member 10 that forms as one by conductivity porous body 11 and resin part (resin portion 92, clathrate frame portion 93) thus by cast gate 74 injections.Conductivity porous body 11 and resin part (resin portion 92, clathrate frame portion 93), because in the pore of the side mouth of conductivity porous body 11, molten resin infiltrates the degree of depth to 5 μ m～1000 μ m and hardens, therefore, by the firm joint of grappling effect.
And, according to the kind of resin, reaction-injection moulding conditions such as selected expulsion pressure or forming temperature.For example,, and cause gas permeability reduction etc., can't bring into play the function of porous body if expulsion pressure is too high, then too much because of potting resin in the conductivity porous body.In addition, if adopt thermoplastic resin, can partly cool off the die surface that is connected in the conductivity porous body, if thermosetting resins such as employing silicon rubber, part heating mould surface can effectively be controlled, and resin infiltrates in the conductivity porous body.
In addition, if the hole diameter or the porosity of conductivity porous body 11 are too small, then molten resin can not infiltrate in the pore, thereby might the grappling effect become insufficient.On the other hand, if the hole diameter or the porosity of conductivity porous body 11 is excessive,, can't bear that ester moulding is pressed and possibility that the compression during hardening of resin and causing is out of shape and have then because insufficient strength.Thereby conductivity porous body 11, its hole diameter are about 10 μ m～2 μ m, the porosity is about 40～98%, for suitable.
And, the material of resin portion 92 and clathrate frame portion 93, be thermoplastic resin, elastomer (containing rubber) but etc. the material of reaction-injection moulding, and do not have conductivity and be advisable, therefore take into full account heat resisting temperature and hardness after, suitably select to get final product.For example, if select soft resin for use, then can improve the sealing of conductivity porous body sidepiece.
Below, with the material of explanation oxygen diffusion electrode 11.As the laminar conductivity porous body that constitutes oxygen diffusion electrode 11, can select carbon system porous bodies such as carbon paper, carbon cloth for use, but can select for use gas diffusibility and conductivity all good and have the metal of three dimensional network ocular structure and be advisable, for example the thin slice of sintering metal powder, metal nonwoven fabrics, folded net etc.Wherein,, can suitably regulate the porosity or thickness as the conductivity porous body of above-mentioned gas diffusion layer member, and the thin slice of the more rich metal dust of the available metal species of sintering, use preferably.And, in metal dust, add behind adhesive, the solvent mixingly, and the doping blowing agent becomes the foaming slurry, then, carries out sintering behind the foaming and molding, it is higher that getable thus foaming metal sintering thin slice can produce the porosity, and more suitable.
At this, the foaming metal sintering method of producing sheet very suitable to oxygen diffusion electrode 11 is described.This foaming metal sintering thin slice is for example to be configured as thin shape by the slurry S that will contain metal dust, is dried into green single G again, burns till that this is green single and make.
Slurry S is, for example, with metal dusts such as SUS316L, organic bond (for example, methylcellulose or hydroxypropyl methylcellulose), solvent (water) mixes, at this, add as required, (for example by the blowing agent of heat treated distillation or vaporization, carbon number be 5～8 water-insoluble hydrocarbon be organic solvent (for example, neopentane, hexane, heptane)) or, defoamer (ethanol) etc.Represent on Figure 12 that by the scraping blade method, being shaped makes slurry S be thin green single manufacturing installation 80.
In green single manufacturing installation 80, at first, the feeding funnel 81 of slurry S is arranged, supplies slurry S on carrying thin slice 83 from storage.Carrying thin slice 83 by roller 82 conveyances, and the slurry S of carrying on the thin slice 83, prolongs between carrying thin slice 83 that moves and scraping blade 84 and is shaped with required thickness.
The slurry S that is shaped is passed through successively by carrying thin slice 83 conveyances, carries out the foaming groove 85 and the heating furnace 86 of heat treated.In foaming groove 85,, therefore can slurry S not cracked, and make the blowing agent foaming owing to be under high humility atmosphere, to carry out heat treated.And,, between particle, form the green single G of the metal dust in cavity by the state of organic bond joint if, then form because of foaming forms empty slurry S drying in heating furnace 86.
Should green single G, after 83 separation of carrying thin slice, in not shown vacuum furnace, carry out degreasing, burn till, remove organic bond thus, can obtain the mutual sintering of each metal dust and become the foaming metal sintering thin slice (conductivity porous body 14) of three dimensional network ocular structure.
And, each illustrated in the above-described embodiment member of formation, its all shapes or compound mode are an example, and in not breaking away from the scope of purport of the present invention, can carry out various changes according to designing requirement.For example, do not adopt the method for reaction-injection moulding to form clathrate frame portion, clathrate bodies such as nonwoven fabrics, resin system net, steel wire, metal nonwoven fabrics, wire netting as built in items, are embedded shaping and also can.That is,, then can produce gas diffusion layer member with material clathrate frame portion different with resin portion if form clathrate frame portion by built in items.
With the relevant gas diffusion layer member 90 of the 4th execution mode in the embodiment of the invention 4 shown in Figure 31; cut apart and be set to two gas-diffusion electrode 91 with oxygen supply face 91a and supply of fuel face 91b; and the sidepiece 91c of its both sides is protected by resin portion 92; simultaneously; oxygen supply face 91a is protected by the sub-frame of trellis portion 93, and is opening by peristome 93a.And each gas- diffusion electrode 91,91 is connected and fixed by connecting portion 94, and supply of fuel face 91b all-round opening.
In this gas diffusion layer member 90, clathrate frame portion 93 is formed by the steel wire (clathrate body) of conductivity material, and for avoiding short circuit phenomenon occurring between the gas-diffusion electrode 91, corresponding each gas- diffusion electrode 91,91 is divided into two settings.And, by the resin portion 92 that non-conductive resin constitutes, being connected in two clathrate frame portions 93 and forming, gas diffusion layer member 90 forms as one thus.
This gas diffusion layer member 90, be that conductivity porous body and clathrate body are embedded shaping as built in items, promptly, with the conductivity porous body as gas-diffusion electrode 91, clathrate body as clathrate frame portion 93, form by the resin of other parts (resin portion 92, connecting portion 94) injection, be fabricated to one.
In addition, before embedding shaping,, conductivity porous body and clathrate body are fixed as one, then in mould, more easily carry out built in items and arrange by modes such as welding.
Embodiment 5
Below according to the execution mode of Figure 32 explanation according to the gas diffusion layer member 10 of the polymer electrolyte fuel cell of the embodiment of the invention 5.
And the representational fuel that is used in above-mentioned polymer electrolyte fuel cell has two kinds of hydrogen and methanol aqueous solutions.When adopting methanol aqueous solution, though the fuel that trickles in the conductivity porous body is liquid, this part is called as gas diffusion layers by convention.At this, comprise the situation of utilizing liquid fuel, be called gas diffusion layers by convention, be not to be defined in gaseous fuel to use.
The structure of this gas diffusion layer member 10 is: have oxygen diffusion electrode (conductivity porous body) 11, keep spacing a plurality of (present embodiment is 4) side by side to the face direction; Resin portion 12 covers the outer peripheral edges of this oxygen diffusion electrode 11; Terminal for connecting portion 3 is connected with oxygen diffusion electrode 11.
The structure of oxygen diffusion electrode 11 is: be provided with, laminar conductivity porous body 14 with three dimensional network ocular structure, and be arranged at a surface of this conductivity porous body 14, and have along the collector body 15 of the two-dimensional mesh ocular structure of face direction prolongation, this collector body 15 infiltrates in surperficial at least a portion of conductivity porous body 14, and conductivity porous body 14 is electrically connected with collector body 15.In the present embodiment, in the surface of conductivity porous body 14, become electrode surface 11a with the reverse side on the surface that is provided with collector body 15.Below, for ease of explanation, in the surface of gas diffusion layer member 10, the surface that is positioned at electrode surface 11a is called the electrode surface 10a of gas diffusion layer member 10.And in the surface of oxygen diffusion electrode 11, it is also passable that the surface that is provided with collector body 15 is called electrode surface 11a.
At this, conductivity porous body 14 is by can suitably regulating the porosity and thickness, and the also abundant foaming metal sintering thin slice of selectable feed metal kind forms.This foaming metal sintering thin plate, as described below, in metal dust, add behind adhesive, the solvent mixingly, and the doping blowing agent forms the foaminess slurry, sintering forms behind the foaming and molding again.
As Figure 32 and shown in Figure 33, collector body 15 is formed by expanded metal or steel wire, and both materials are SUS316L.
When utilizing expanded metal, in Figure 33, the LW value is about 3.0mm, the SW value is 0.2mm for 1.0mm, W value for 0.6mm, thickness; When adopting steel wire, line directly is 0.05mm, 50 meshes～300 meshes.
Portion of terminal 3 does not but have the lamellar hardware of gas permeability for tool conductivity, and is engaged in the side 15a of collector body 15 by the spot welding mode.
As mentioned above, in the present embodiment, adopted foaming metal sintering thin slice, in addition, also can select metal nonwoven fabrics or carbon system porous bodies such as carbon paper, carbon cloth for use as conductivity porous body 14.But, be used for the conductivity porous body 14 of polymer electrolyte fuel cell owing to require to have good gas diffusibility and conductivity, so foaming metal sintering thin slice, metal nonwoven fabrics, and folded net etc. for suitable.Wherein, foaming metal sintering thin slice as mentioned above, not only can suitably be regulated the porosity and thickness, and can select for use the feed metal kind also a lot, and also can produce high porosity, and is therefore more suitable.
In addition, select expanded metal or steel wire for use with collector body 15, but be not limited to these, also can select punch metal (punching metal) etc. for use.That is, have the conductivity to face direction and thickness direction, especially the conductivity to the face direction is better than conductivity porous body 14 (resistance is little), and has the gas permeability of thickness direction, that is, have the two-dimensional mesh ocular structure that prolongs to the face direction and get final product.
In addition, when gas diffusion layer member 10 is used for polymer electrolyte fuel cell, because in portion of terminal 3, conductivity porous body 14 and the collector body 15, the electronics that trickling is produced by electrode reaction, therefore, these each members 3,14～15 preferably adopt resistant materials such as stainless steel.
Figure 34 is main sectional view of the polymer electrolyte fuel cell 200 of suitable this gas diffusion layer member 10.
The structure of this fuel cell 200 is: have a pair of gas diffusion layer member 10 (A), 10 (B); And the dielectric substrate of between electrode surface 10a, the 10a of this a pair of gas diffusion layer member 10 (A), 10 (B), clamping 121; The utmost point A that acts as a fuel is to the fuel supplies 40 of gas diffusion layer member 10 fuel supplying of a side.Dielectric substrate 121 is that polyelectrolyte membrane constitutes by fluororesin for example, has in film, allows hydrogen ion to move, and the character that does not allow electronics to pass through.And the opposite side of a pair of gas diffusion layer member 10 (A), 10 (B) is air pole B.
The structure of fuel electrodes A is: the electrode surface 11a of each fuel diffusion electrode (conductivity porous body) 11, by catalyst layer C, be connected with dielectric substrate 121, and simultaneously, this electrode surface 11a and reverse side and are used to preserve and the fuel supplies 40 of fuel supplying is connected.Catalyst layer C is by on the electrode surface 11a surface of fuel diffusion electrode 11, and coating comprises to be supported platinum series catalysts atomic carbon particle polyelectrolyte solution and form.
Be provided with each 4 gas-diffusion electrode 11 respectively at fuel electrodes A and air pole B, clamp dielectric substrate 121, be positioned at the portion of terminal 3 that this is connected with the gas-diffusion electrode 11 on direction next door, 16 link to each other by connecting up, so that the portion of terminal 3 by being arranged at these electrodes 11 separately is connected with the direction series connection to gas-diffusion electrode 11.And, be positioned at the portion of terminal 3 at the two ends of above-mentioned series connection, in this fuel cell 200, can carry out the function of anode 201, negative electrode 202 respectively.
Fuel supplies 40 is preserved fuel (nail alcoholic solution here), and it constitutes: the porous matter portion 41 by constituting to the felt of fuel electrodes A fuel diffusion electrode 11 fuel supplying etc. is covered by resin frame 42.And the porous matter portion 41 of fuel supplies 40 is connected with the collector body 15 of fuel electrodes A fuel diffusion electrode 11, therefore, the fuel that is stored in porous matter portion 41 can be supplied in fuel diffusion electrode 11 by infiltrating to press.In addition, the resin frame 42 of fuel supplies 40 and the resin portion 12 of gas diffusion layer member 10 are for example fixed by the ultrasonic wave juncture.
Promptly, in this polymer electrolyte fuel cell 200, the gas-diffusion electrode 11 of fuel electrodes A and air pole B, conductivity porous body 14 with three dimensional network ocular structure, have gas permeability and conductivity, and the collector body 15 with two-dimensional mesh ocular structure also has gas permeability and conductivity, especially, have hold concurrently in the conductivity of face direction so-called gas diffusion layers and collector plate.
In addition, catalyst layer C at this, coats the electrode surface 11a of gas-diffusion electrode 11 and forms, still, because its interface that is arranged at gas-diffusion electrode 11 and dielectric substrate 121 get final product, therefore also can be in the formation of the surface of dielectric substrate 121.
As mentioned above in the fuel cell 200 of Gou Chenging, be supplied in hydrogen the fuel of fuel diffusion electrode 11 of fuel electrodes A side, on catalyst layer C,, and dielectric substrate 121 shifted to air pole B by electrode reaction generation ionization from fuel supplies 40.And, after hydrogen ion arrival is clamped the air pole B that is arranged in opposite side with dielectric substrate 121, at the interface of dielectric substrate 121 with catalyst layer C, with the oxygen in oxygen diffusion electrode 11 electrode surface 11a and the surperficial from the negative air supplied, the generating electrodes reaction also generates water.
On the other hand, by the electronics of hydrogen ion generation,, shift to air pole B by portion of terminal 3 from fuel electrodes A by the loop (not shown) of being located at gas diffusion layer member 10 outsides.And, move by this electronics, can produce above-mentioned electric energy.
At this, illustrate gas-diffusion electrode 11 fit closely foaming metal sintering method of producing sheet.This foaming metal sintering thin slice is for example to be configured as thin shape by the slurry S that will contain metal dust, is dried into green single G again, burns till that this is green single and make.
Slurry S is, for example (for example with metal dusts such as SUS316L, organic bond, methylcellulose or hydroxypropyl methylcellulose), solvent (water) mixes, at this, add as required, the blowing agent that distils or vaporize by heat treated (for example, carbon number be 5～8 water-insoluble hydrocarbon be organic solvent (for example, neopentane, hexane, heptane)) or defoamer (ethanol) etc.Figure 12 represents to make slurry S form green single manufacturing installation 80 of thin shape by the scraping blade method.
In green single manufacturing installation 80, at first, the feeding funnel 81 of slurry S is arranged, supplies slurry S on carrying thin slice 83 from storage.Carrying thin slice 83 by roller 82 conveyances, and the slurry S of carrying on the thin slice 83, prolongs between carrying thin slice 83 that moves and scraping blade 84 and is shaped with required thickness.
The slurry S that is shaped, foaming groove 85 and the heating furnace 86 by carrying out heat treated successively by carrying thin slice 83 conveyances.In foaming groove 85, owing under high humility atmosphere, carry out heat treated, therefore can slurry S not cracked, make the blowing agent foaming.And, dry in heating furnace 86 as if the slurry S that forms the cavity because of foaming, then form and form the green single G of empty metal dust between particle by the state of organic bond joint.
Should green single G, after 83 separation of carrying thin slice, in not shown vacuum furnace, carry out degreasing, burn till, remove organic bond thus, can obtain the mutual sintering of each metal dust and become the foaming metal sintering thin slice (conductivity porous body 14) of three dimensional network ocular structure.
Below, the gas diffusion layer member manufacture method relevant with embodiment of the present invention is described.
The method is, with portion of terminal 3, conductivity porous body 14, and collector body 15 as built in items, embed shaping.Here, for a gas diffusion layer member 10, embed 4 groups of portion of terminal 3, conductivity porous body 14, reach collector body 15.
At first embed the simple structure of die assembly for molding 400 in order to embed to be shaped according to Figure 35 and 36 explanations.
The structure of this embedding die assembly for molding 400 is: have the relative summary to a pair of moveable die 401 that is provided with and fixed mould 402 with fixed mould face 402a of moveable die face 401a and constitute, and moveable die 401 can be advanced and retreat to move to fixed mould 402 and be supported.In addition, moveable die 401 advances when forming the matched moulds state to fixed mould 402, will form die cavity 403 between each die face 401a, 402a.And, though not expression among the figure for the alignment pin of above-mentioned built in items along the direction location on die face 401a, 402a surface, can be supported on the surface of moveable die face 401a with haunting.
By the embedding die assembly for molding 400 that constitutes as mentioned above, when forming gas diffusion layer member 10 shown in Figure 32, at first, in advance in the end face 15a of collector body 15 solder terminal portion 3, and, at 4 of collector body 15 surperficial stacked arrangement conductivity porous bodies 14, be aligned in moveable die face 401a and go up the outstanding position of above-mentioned alignment pin wherein, keep spacing to the face direction mutually, the surface of collector body 15 and portion of terminal 3 is contacted with moveable die face 401a.
At this, the thickness summation of the thickness of conductivity porous body 14 and collector body 15, die cavity 403 degree of depth that form during greater than matched moulds (the switch direction size of mould) particularly, are set at, than the degree of depth of die cavity 403, the thickness of big collector body 15.
Below, moveable die 401 before fixed mould 402 and then carry out matched moulds, and is formed die cavity 403.At this moment, as mentioned above, because the size of the stacking direction of conductivity porous body 14 and collector body 15 is set at, greater than the degree of depth of die cavity 403, therefore, during matched moulds, conductivity porous body 14 all connects airtight with moveable die face 401a with fixed mould face 402a, collector body 15 and engages, simultaneously, conductivity porous body 14 makes conductivity porous body 14, collector body 15, portion of terminal 3 firm fixing between die face 401a, 402a to the plastic deformation of matched moulds direction.And, at this moment, make 14 compressions 3～90% of conductivity porous body, therefore by conductivity porous body 14 porosity adjustment of the gas diffusion layer member 10 that constitutes manufacturing, simultaneously, in more than 15 hole of collector body that constitutes the two-dimensional mesh ocular structure, conductivity porous body 14 is under indivedual states that infiltrate, conductivity porous body 14 is connected with collector body 15, and, intimate engagement between 14,15 facing surfaces of each member.
And, with above-mentioned alignment pin moveable die face 401a retreat move after, will be from the molten resin 406 of runner 404 by cast gate 405 injections, being filled in the die cavity 403, is gas diffusion layer member 10 thereby form by conductivity porous body 14, collector body 15, portion of terminal 3 with the embedding formed products that resin portion 12 becomes one.
In addition, according to the resin kind, can suitably select reaction-injection moulding conditions such as expulsion pressure or forming temperature.For example,, and cause gas permeability reduction etc., can't bring into play the function of conductivity porous body if expulsion pressure is too high, then too much because of potting resin in the conductivity porous body.In addition, during as if the employing thermoplastic resin, can partly cool off the die surface that is connected in the conductivity porous body, if thermosetting resins such as employing silicon rubber, part heating mould surface can effectively be controlled, and resin infiltrates in the conductivity porous body.Particularly, for example,, when adopting polypropylene, be 180 ℃, 80kN matched moulds with forming temperature as resin portion 12, press the 250kg/cm2 reaction-injection moulding to be shaped, can obtain this gas diffusion layer member 10.
As mentioned above, according to the gas diffusion layer member in the present embodiment 10,, therefore, can realize the good state that is electrically connected of conductivity porous body 14 and collector body 15 because collector body 15 infiltrates in the surface of conductivity porous body 14.And,, therefore, will can conduct well to the face direction by this collector body 15 at the electric current of polymer electrolyte fuel cell 200 generations because collector body 15 has the two-dimensional mesh ocular structure that prolongs to the face direction.
Can produce little, the high-power polymer electrolyte fuel cell 200 of resistance therefrom.
And, because the outer peripheral edges resin portion 12 at conductivity porous body 14 forms as one, therefore, can seek the raising of the operability of this gas diffusion layer member 10, the packing engineering when utilizing these gas diffusion layer member 10 assembling solid high molecular fuel batteries 200 can also be shortened, the raising of precision can also be sought to assemble.
And, because collector body 15 has the two-dimensional mesh ocular structure that prolongs to the face direction, therefore, can make the electric current that produces at polymer electrolyte fuel cell 200, can conduct well to the face direction by collector body 15.
Especially, in the present embodiment, be not only the outer peripheral edges of conductivity porous body 14, and in the outer peripheral edges of collector body 15, resin portion 12 also forms as one, and therefore, these conductivity porous bodies 14 are connected each facing surfaces much at one with collector body 15, simultaneously, also can keep this connection status for a long time.And, at this moment, also can keep the connection status of conductivity porous body 14 and collector body 15 for a long time.And collector body 15 infiltrates in the surface of conductivity porous body 14, can suppress the resistance between conductivity porous body 14 and the collector body 15 to greatest extent, therefore, the high powerization of polymer electrolyte fuel cell 200 can be sought, simultaneously, the long lifetime of above-mentioned battery 200 can be sought.And, because resin portion 12 is set, and can only process resin portion 12, it is fixing with shapes such as holes to be easy to generate device.
According to the gas diffusion layer member manufacture method in the present embodiment, conductivity porous body 14 and collector body 15 are being compressed under the fixing state to stacking direction, in die cavity 403, spray molten resin 406, therefore, by the expulsion pressure of the molten resin in die cavity 403 406, can suppress conductivity porous body 14 and collector body 15 position deviation along die face 401a, 402a direction.
And, during matched moulds, to the thickness direction plastic deformation, simultaneously,, therefore, conductivity porous body 14 is infiltrated in the hole on collector body 15 surfaces conductivity porous body 14 because collector body 15 has the two-dimensional mesh ocular structure.Thereby, can realize easily the same connection status of described conductivity porous body 14 and collector body 15 simultaneously, effectively suppressing position deviation.
And, because conductivity porous body 14 and fixed mould face 402a, collector body 15 and moveable die face 401a be under the state of intimate engagement separately, injection molten resin 406 die cavity 403 in, therefore, can suppress this resin 406 and penetrate between 14,402, and 15, between the 401a.
Thus, can form, can suppress the gas diffusion layer member 10 of resistance between conductivity porous body 14 and the collector body 15 to greatest extent with efficient, high precision.
Particularly, as collector body 15, when adopting punch metal, in the manufacture process of punch metal, the edge part of the through hole on a surface of outside in the collector body 15 is from this protrusion of surface.Therefore,, make under the state of above-mentioned side surface subtend layout, during with collector body 15 compressions, collector body 15 can be infiltrated well on the surface of conductivity porous body 14 on the surface of conductivity porous body 14.
According to the gas diffusion layer member manufacture method in the present embodiment, during matched moulds, collector body 15 is infiltrated in the surface of conductivity porous body 14, therefore, when spraying, can realize the state of the intimate engagement on die face 401a, 402a and above-mentioned built in items surface.Therefore, can effectively stop molten resin 406 to infiltrate between die face 401a, 402a and built in items surface, or the built in items position deviation that takes place because of expulsion pressure.Thus, can effectively realize the state that is electrically connected that collector body 15 and conductivity porous body 14 are good, simultaneously, not cause manufacturing defect, can form the gas diffusion layer member 10 of high precision.
Particularly, as collector body 15, when adopting punch metal, in the manufacture process of punch metal, the edge part of the through hole on a surface of outside in the collector body 15 is from this protrusion of surface.Therefore,, make under the state of above-mentioned one surperficial subtend layout, during with collector body 15 compressions, collector body 15 can be infiltrated well on the surface of conductivity porous body 14 on the surface of conductivity porous body 14.
And the part that is connected with resin portion 12 at conductivity porous body 14 is because in the pore of conductivity porous body 14 side mouth, molten resin infiltrates to the degree of depth of about 5 μ m～1000 μ m and hardens, therefore, by the grappling effect, can make conductivity porous body 14 and 12 firm connections of resin portion.And,, therefore, can seek to improve the connection high strength and the long lifetime of gas diffusion layer member 10 each member that constitute by conductivity porous body 14, collector body 15, resin portion 12 because collector body 15 infiltrates the surface of conductivity porous body 14.
Each illustrated in the above-described embodiment member of formation, its all shapes or compound mode etc. are an example just, and in the scope that does not break away from purport of the present invention, can carry out various changes according to designing requirement.
For example, in the above-described embodiments, the material of resin portion 12 has been selected thermoplastic resin for use, is limited to these but have more than.That is, resin portion 12 can select elastomer (containing rubber) for use but etc. the material of reaction-injection moulding, and do not have conductivity and gas permeability gets final product, therefore, can after taking into full account heat resisting temperature and hardness, can suitably select this.If adopt soft resin, can improve sealing.
And resin portion 12 and portion of terminal 3 can be shaped by double-colored forming process.That is, reaction-injection moulding electroconductive resin and form portion of terminal 3, the reaction-injection moulding non-conductive resin also can and form resin portion 12 afterwards.
And, state on the implementation embed to be shaped before, in advance to conductivity porous body 14 and collector body 15, weld, spot welding or diffusion connect also passable.At this moment, can effectively be suppressed at and spray in the die cavity 403 before the molten resins 406, above-mentioned alignment pin is retreated the conductivity porous body 14 that takes place when mobile and the relative position deviation of collector body 15.
And, when utilizing gas diffusion layer member 10 to form polymer electrolyte fuel cell, can the surface that be provided with these member 10 collector bodies 15 is also passable as electrode surface 11a.
And in the above-described embodiment, the formation that the both sides' outer peripheral edges portion of conductivity porous body 14 and collector body 15 of being illustrated in forms as one resin portion 12 still, as shown in figure 37, only forms resin portion 12 in the outer peripheral edges portion of conductivity porous body 14 and also can.At this moment, also can shorten the fuel cell assembling engineering of utilizing gas diffusion layer member 10, can improve assembling precision again.
And, collector body 15 is infiltrated the method for making gas diffusion layer member 10 in conductivity porous body 14 surfaces, have more than the method that is limited to aforesaid execution mode with 14 plastic deformations of conductivity porous body.For example, also can following manufacturing gas diffusion layer member 10.
At first, according to Figure 38 and 39 easy structure of carrying out this manufacturing installation is described.The structure of this device is: have slurry tank 310 and be used for filling paste S; And above slurry tank 310 upper end open portions, be provided with and scrape part 320; The not shown foaming groove slurry S that is used to foam, and form foaming body; Not shown drying oven is used for the above-mentioned foaming body of dried; Not shown compression roller is used for the foaming body of extruded dried; Firing furnace portion is used for degreasing, burns till the foaming body through extruding; Not shown collector body running tool is used to move long collector body 15.Here, the collector body running tool has not shown a plurality of rollers of being reeled and being formed by long collector body 15, and each inscape 310,320... that this collector body 15 makes said apparatus are continuously, pass through successively.
To scraping part 320, constitute outside in by the collector body in the slurry tank 310 15 is wiped off with the tight attached slurry S of built-up welding state, inside and outside at collector body 15 in the face of a pair of to being provided with, but its spacing position is adjusted.And make this a pair of distance of scraping between part 320 front ends, be made as thickness, and scrape the front end of part 320 by this less than collector body 15, with slurry S, in a plurality of holes of the collector body 15 that constitutes the two-dimensional mesh ocular structure (below, be called for short " mesh "), the outside is filled in each from it.Thereby,, scrape part and also this emptying aperture can be removed from slurry S even tightly invest when comprising emptying aperture among the slurry S of collector body 15.At this moment, scraping part 320 selects for use the elastomeric material with flexibility to be advisable.
The structure of above-mentioned compression roller is: the rotating shaft rotation of the level that prolongs to the Width of the collector body 15 that is in running status, rotatable support makes the above-mentioned collector body 15 that is in running status, lateral surface rotation and pushing in it.
The structure of above-mentioned firing furnace portion is, has the not shown debinding furnace of degreasing foaming body, and the firing furnace 330 that burns till the foaming body of degreasing, and the inside of firing furnace 330 is provided for the power application roll portion 340 of foamable body simultaneously.
The structure of power application roll portion 340 is, in firing furnace 330, be in the rotating shaft rotation of the level that 15 Widths of collector body of running status prolong, rotatable support, simultaneously, join, be provided with herein and make the electric current trickling with above-mentioned foaming body in the above-mentioned mesh that is filled in collector body 15, promptly by a pair of power application roll 340A of energising heating, and be power supply 340B to this power application roll 340A supply of current.Power application roll 340A is with respect to the traffic direction F of collector body 15, in many places (in Figure 39, with respect to traffic direction F, front side and rear side two places) be provided with, and each roller 340A..., the interior outside with collector body 15 and above-mentioned foaming body joins with whole Width.
According to above-mentioned manufacturing installation, the manufacture method of gas diffusion layer member 10 is described below.
As shown in figure 38, from slurry tank 310 bottoms of filling paste S, to the long collector body 15 of these groove 310 inner insertions, afterwards, and this collector body 15 of side shifting that makes progress, 310 upper end open portions extract collector body 15 from slurry tank.At this moment, in the interior outside of long collector body 15, slurry S tightly adheres to the built-up welding state.Afterwards, this collector body 15 is moved upward again, and, wipes the slurry S that adheres to the built-up welding state above-mentioned off by being arranged at more a pair of part 320 tips of scraping of top of slurry tank 310 upper end open portions.
Afterwards, the collector body 15 with slurry S is moved more and make it by above-mentioned foaming groove.In this foaming groove, humidity is made as under the high humility atmosphere 65% or more, with 25 ℃～80 ℃ heating slurry S, the blowing agent that the slurry S that foams comprises.At this moment, owing to humidity is set at more than 65%, so be full of cracks foaming does not well take place in slurry S.And this moment, a side surface of collector body 15 is fixed in section in the above-mentioned foaming groove, the opposite side surface is then fixing, thereby, being filled in the slurry S in the collector body 15 above-mentioned meshes, will come from opposite side surface bulging.
Afterwards, make and have foaming slurry S the collector body 15 of (below, be called for short foaming body), move more and make it pass through above-mentioned drying oven.In this drying oven, for example by far-infrared lamp formula heater, with 30 ℃～150 ℃ heating, simultaneously, to its inner supply with above-mentioned by far-infrared lamp formula heater heats temperature dry air much at one.Under this environment, above-mentioned foaming body is dried, and is produced the metal dust in cavity between particle by above-mentioned foaming, by engaging under the effect of organic bond.
Then, make collector body 15, move more and make it pass through above-mentioned compression roller with this foaming body.Thereby by slurry S foaming, even from the above-mentioned opposite side surface of collector body 15, foaming body also can squeeze broken this bulging part, and can adjust the thickness or the porosity of foaming body during with unrestricted state bulging in above-mentioned foaming groove.
Afterwards, make collector body 15, move more and make it pass through above-mentioned firing furnace portion with foaming body that thickness or the porosity adjust.At this moment, make it earlier by above-mentioned debinding furnace.In this debinding furnace, its internal temperature is set at 400 ℃～7000 ℃, and simultaneously, when the metal dust that is contained as slurry S was SUS316L powder or Ti powder, inside became reducing atmosphere or vacuum atmosphere.
Afterwards, the foaming body of this degreasing is moved more and make it pass through above-mentioned firing furnace 330.In this firing furnace 330, when its inside became reducing atmosphere, inert atmosphere or vacuum atmosphere, when slurry S was the SUS316L powder, its temperature inside was with 1100 ℃～1350 ℃ settings.And the power application roll 340A that is provided with by mode as mentioned above in these firing furnace 330 inside makes the whole position trickling electric current along above-mentioned foaming body surface direction and thickness direction, and this this foaming body produces Joule heat, and burns till foaming body by this heat.Above-mentioned therefrom adhesive is removed and each metal dust phase sintering, forms the conductivity porous body 14 with three dimensional network ocular structure, simultaneously, is formed on the above-mentioned mesh of collector body 15, the long gas diffusion layer member that conductivity porous body 12 engages.Afterwards, after should long gas diffusion layer member cutting off, carry out aforesaid inserts reaction-injection moulding, and form Figure 32 or gas diffusion layer member 10 shown in Figure 37 by institute's measured length.
At the gas diffusion layer member 10 that forms as mentioned above, the same with aforementioned execution mode, can infiltrate collector body 15 at conductivity porous body 14, special simultaneously, can engage the above-mentioned mesh of collector body 15 with conductivity porous body 14.Thereby collector body 15 just can firmly closely be connected with conductivity porous body 14, thereby can these good states that are electrically connected of 14,15 of more reliable realization.
And, in the above-described embodiment, when making gas diffusion layer member 10, behind the above-mentioned foaming body of above-mentioned kiln dried, before carrying out degreasing by above-mentioned firing furnace portion, burning till, push above-mentioned foaming body by above-mentioned compression roller, but this extruding can get final product according to concrete needs, be not necessary to carry out.And, in the manufacture method of present embodiment, as the mode of infiltrating collector body 15 on the surface of conductivity porous body 14, except that the mode shown in Figure 32 and 37, can also be in the thickness of conductivity porous body 14 mode less than the thickness of collector body 15, or in conductivity porous body 14 inside, the mode that collector body 15 is imbedded fully realizes.
Embodiment 6
Figure 40 represents the main portion according to the polymer electrolyte fuel cell that utilizes gas diffusion layer member 10,50,60 of embodiments of the invention 6.This fuel cell has the so-called stacked structures that piles up 4 groups of cell unit 131, thus along with fuel supplying (for example, methanol aqueous solution) with as the air of oxidant, the generating electrodes reaction, thus electric power can be produced.
As shown in figure 40, the structure of gas diffusion layer member 10 is: gas- diffusion electrode 11,11 and dividing plate 122 pile up to thickness direction, and the resin frame 13 that covers around its face direction is set to one.And, shown in Figure 40 and 41, in this gas diffusion layer member 10, connect resin frame 13 and be provided with, first flow 10a, the 10b of the first fluid (fuel) that is used to circulate and being used to the circulate second runner 10c, the 10d of second fluid (air).
In addition, Figure 41 be in Figure 40 along the target view of II-II line, Figure 40 is along the cross section target view of I-I line in Figure 41.
The structure of gas-diffusion electrode 11 is: the thin plate by the conductivity porous body with three dimensional network ocular structure constitutes, because of the pore at surface opening is communicated with all directions, and have gas permeability, and have the characteristic light, that surface area is big in addition.This gas-diffusion electrode 11 forms: be provided with the joint shape in the electrode body 11a end that slightly is brachmorphy and be used for connecting any one connecting portion 11b, 11b of first flow 10a, 10b and the second runner 10c, 10d.
In each gas- diffusion electrode 11,11, make electrode body 11a overlapping, and connecting portion 11b, 11b overlaid are arranged.And among first flow 10a, the 10b and the second runner 10c, 10d of connecting portion 11b and perforation resin frame 13, any one runner links to each other.That is, in gas-diffusion electrode 11,, connecting different runners respectively being arranged at the two connecting portion 11b of place of electrode body 11a.
Thereby, be supplied in the fuel of first flow 10a, by the connection pore of fuel diffusion electrode 11, flow out from first flow 10b, and, be supplied in the air of the second runner 10c, by the connection pore of oxygen diffusion electrode 11, flow out from first flow 10d.
The structure of dividing plate 122 is: by not allowing gas or fluid as air or fuel to pass through, and for example have conductivity, with carbon plate or metallic plate etc. with corrosion resistance, form at least greater than the overlapping H font of two gas-diffusion electrodes 11,11.And, be arranged between the gas- diffusion electrode 11,11, with flowing of fluid between each electrode of effective prevention, and, as shown in figure 40, the cell unit 131 that each gas- diffusion electrode 11,11 of connecting forms.
And gas-diffusion electrode 11 and dividing plate 122 can be tight attached fixing by diffusion bond.
Cover around the face direction of the gas-diffusion electrode 11 that resin frame 13 is piled up thickness direction, dividing plate 122 and gas-diffusion electrode 11, be set to one, and its two sides constitutes with one side with the surface of gas- diffusion electrode 11,11 is continuous.This resin frame 13 in its four angles, is provided with the bolt insertion hole 10e that connects to thickness direction to imbed the cube shaped one-tenth of roughly one-tenth of oxygen diffusion electrode 11 and dividing plate 122.And, in bolt insertion hole 10e, be used for fixing these tie bolts in the time of can inserting logical a plurality of gas diffusion layer members 10 and dielectric substrate 121 multiple-level stacks.
In addition, in the both ends of the surface of fuel cell, be respectively equipped with gas diffusion layer member 50,60.
As Figure 40 and shown in Figure 42, the structure of gas diffusion layer member 50 is: fuel diffusion electrode 51 and dividing plate 152 pile up to thickness direction, and the resin frame 53 that covers around its face direction is set to one.And, in this gas diffusion layer member 50, connect resin frame 53 at fuel diffusion electrode 51 and be provided with and be used to circulate first flow 50a, the 50b of first fluid (fuel), and the second runner 50c, the 50d of second fluid (air) that is used to circulate.
The same with oxygen diffusion electrode 11, the structure of fuel diffusion electrode 51 is: the thin plate that is made of the conductivity porous body with three dimensional network ocular structure, because of the pore at surface opening is communicated with all directions, and have gas permeability, have the characteristic light, that surface area is big in addition.This fuel diffusion electrode 51 is provided with connecting portion 51b, the 51b that is used to connect the second runner 50a, 50b in slightly rectangular electrode body 51a end with the joint shape.
Thereby, be supplied in the fuel of runner 50a, by the connection pore of fuel diffusion electrode 51, flow out from runner 50b.
The same with dividing plate 122, the structure of dividing plate 152 is: by not allowing gas or fluid as air or fuel to pass through, and for example have conductivity, with carbon plate or metallic plate etc. with corrosion resistance, form at least greater than the surface that covers fuel diffusion electrode 51.And the layout that links to each other with fuel diffusion electrode 51, thereby stop from the circulation of fuel diffusion electrode 51 to the fluid of outside batteries.
In addition, fuel diffusion electrode 51 and dividing plate 152 can be tight attached fixing by the diffusion bond mode.
Cover around the fuel diffusion electrode 51 that resin frame 53 is piled up thickness direction and the face direction of dividing plate 152, be set to one, and one of them face links to each other with the surface of fuel diffusion electrode 51 and constitutes with one side.This resin frame 53 in its four angles, is provided with the bolt insertion hole 50e that connects to thickness direction to imbed the cube shaped one-tenth of roughly one-tenth of fuel diffusion electrode 51 and dividing plate 152.And, in bolt insertion hole 50e, be used for fixing these tie bolts in the time of can inserting logical a plurality of gas diffusion layer members 10,50 and dielectric substrate 121 multiple-level stacks.
As Figure 40 and shown in Figure 43, the structure of gas diffusion layer member 60 is: oxygen diffusion electrode 61 and dividing plate 162 pile up at thickness direction, and the resin frame 63 that covers around its face direction is set to one.And, in this gas diffusion layer member 60, be positioned at circulate first flow 60a, the 60b and being used to of first fluid (fuel) the circulate second runner 60c, the 60d of second fluid (air) of being used to of oxygen diffusion electrode 61, connect resin frame 63 and be provided with.
The same with oxygen diffusion electrode 11,51, the structure of oxygen diffusion electrode 61 is: the thin plate that is made of the conductivity porous body with three dimensional network ocular structure, because of the pore at surface opening is communicated with all directions, and have gas permeability, have the characteristic light, that surface area is big in addition.This oxygen diffusion electrode 61 is provided with connecting portion 61b, the 61b that is used to connect the second runner 60c, 60d in slightly rectangular electrode body 61a end with the joint shape.
Thereby, be supplied in the air of runner 60c, by the connection pore of oxygen diffusion electrode 61, flow out from runner 60d.
The same with dividing plate 122,152, the structure of dividing plate 162 is: by not allowing gas or fluid as air or fuel to pass through, and for example having conductivity, carbon plate or the metallic plate etc. with corrosion resistance form at least greater than the surface that covers oxygen diffusion electrode 61.And the layout that links to each other with oxygen diffusion electrode 61, thereby stop from the circulation of oxygen diffusion electrode 61 to the fluid of outside batteries.In addition, oxygen diffusion electrode 61 and dividing plate 162 can be tight attached fixing by the diffusion bond mode.
Cover around the oxygen diffusion electrode 61 that resin frame 63 is piled up thickness direction and the face direction of dividing plate 162, be set to one, and one of them face links to each other with the surface of oxygen diffusion electrode 61 and constitutes with one side.This resin frame 63 in its four angles, is provided with the bolt insertion hole 60e that connects to thickness direction to imbed the cube shaped one-tenth of roughly one-tenth of oxygen diffusion electrode 61 and dividing plate 162.And, in bolt insertion hole 60e, be used for fixing these tie bolts in the time of can inserting logical a plurality of gas diffusion layer members 10,50,60 and dielectric substrate 121 multiple-level stacks.
In fuel cell shown in Figure 40, tightly invest gas diffusion layer member 10,50,60 gas- diffusion electrodes 11,51,61 and the dielectric substrate 121 of layout, can be that polymer electrolytic film forms for example by fluororesin.Dielectric substrate 121 has, in film hydrogen ion movably, and the character that does not allow electronics to pass through.Be formed with at dielectric substrate 121, through hole 20a, this through hole is when when overlapping, being communicated in first flow 10a, 10b, 50a, 50b, 60a, 60b and the second runner 10c, 10d, 50c, 50d, 60e, 60d with gas diffusion layer member 10,50,60.
At the interface (in the present embodiment be the face side of gas- diffusion electrode 11,51,61) of this dielectric substrate 121, be provided with catalyst layer 31 with gas diffusion layer member 10,50,60 gas- diffusion electrodes 11,51,61.
In addition, catalyst layer 31 can be got involved between dielectric substrate 121 and gas- diffusion electrode 11,51,61, and in the present embodiment, catalyst layer 31 is the surfaces that are positioned at gas- diffusion electrode 11,51,61, but also can form on dielectric substrate 121 surfaces.
Fuel cell structure shown in Figure 40 is: pile up above-mentioned gas diffusion layer member 10,50,60 and be arranged in dielectric substrate 121 between it, and its both sides are as the barricade of no gas permeability and conductivity, with dividing plate 152,162 sealings that are arranged at gas diffusion layer member 50,60.Therefore the gas diffusion layer member 10,50,60 that becomes one by resin frame 13,53,63 because easy to operate, cracky not, can produce not that cracky is scrapped, operable automatically, the good fuel cell of productivity.
In this fuel cell,, be formed with: be communicated with first flow 10a, 50a, 60a and through hole 20a and the fuel-side service duct F that forms by piling up gas diffusion layer member 10,50,60 and dielectric substrate 121; The fuel-side discharge-channel (not shown) that is communicated with first flow 10b, 50b, 60b and through hole 20a and forms; The air side service duct A that is communicated with the second runner 10c, 50c, 60c and through hole 20a and forms; The air side discharge-channel (not shown) that is communicated with the second runner 10d, 50d, 60d and through hole 20a and forms.
In fuel cell, during from fuel-side service duct F fuel supplying (nail alcoholic solution here), by first flow 10a, 50a, 60a, in each oxygen diffusion electrode (fuel electrodes) 11,51 fuel supplying.And, this fuel is by in the oxygen diffusion electrode 11,51 time, by the catalyst reaction on the interface of catalyst layer 31, the hydrogen generation ionization in the fuel, remaining fluid (non-reacted parts) then emits from the fuel-side discharge-channel by first flow 10b, 50b.
On the other hand, from air side service duct A, by the second runner 10c, 50c, 60c, at subtend each oxygen diffusion electrode (air pole) 11,61 supply air in fuel electrodes 11,51.And, at fuel electrodes 11,51 Ionized hydrogen, mobile dielectric substrate 121 and arrive air pole 11,61, and on catalyst layer 31 interfaces of air pole 11,61, by electrode reaction and airborne oxygen reaction generation water.The water that generates emits from the air side discharge-channel by the second runner 10d, 60d.In addition, the gas (non-reacted parts) that is left in air after the electrode reaction also by the second runner 10d, 60d, emits by the air side discharge-channel.
By the electronics that takes place from electrification of hydrogen, shift to air pole (oxygen diffusion electrode) 11 from fuel electrodes (fuel diffusion electrode) 11 by dividing plate 122.By this movement of electrons, fuel cell is an anode with fuel electrodes 51, and air pole 61 is a negative electrode, can produce above-mentioned electric energy.
But in this polymer electrolyte fuel cell, gas- diffusion electrode 11,51,61 is, because of having gas permeability and conductivity by the three dimensional network ocular structure, and the sheet-like member of hold concurrently gas diffusion layers and collector plate.Form the conductivity porous body of this gas- diffusion electrode 11,51,61, can select carbon system porous bodies such as carbon paper, carbon cloth for use, but select for use gas diffusibility and conductivity all good, and have the metallic material of three dimensional network ocular structure, be advisable as sintering metal powder thin slice, metal nonwoven fabrics, folded net etc.Can suitably regulate the porosity and thickness, and the thin slice of the also abundant metal dust of the available feed metal kind of sintering, as the conductivity porous body of this gas diffusion layer member, more suitable.
In addition, adding in metal dust behind adhesive, the solvent of foaming metal sintering thin slice is mixing, and the doping blowing agent forms the foaminess slurry, again with sintering behind this foaminess slurry foaming and molding, produce foaming metal sintering thin slice thus, connecting high porosity therefrom can produce, so more suitable.
In the present embodiment, adopted and can suitably regulate the porosity and thickness, and the also abundant foaming metal sintering thin slice of available feed metal kind.
The manufacture method of foaming metal sintering thin slice is described below with reference to Figure 12.
The manufacturing process of foaming metal sintering thin slice is, at first adds behind adhesive, the solvent mixingly in metal dust, and the doping blowing agent forms foaminess slurry S, with sintering behind this foaminess slurry foaming and molding, produces foaming metal sintering thin slice thus again.
Slurry S is, for example (for example with metal dusts such as SUS316L, organic bond, methylcellulose or hydroxypropyl methylcellulose), solvent (water) mixes, at this, add as required, the blowing agent that distils or vaporize by heat treated (for example, carbon number be 5～8 water-insoluble hydrocarbon be organic solvent (for example, neopentane, hexane, heptane)) or defoamer (ethanol) etc.Figure 12 represents to make slurry S form green single manufacturing installation 80 of thin shape by the scraping blade method.
In green single manufacturing installation 80, at first, the feeding funnel 81 of slurry S is arranged, supplies slurry S on carrying thin slice 83 from storage.Carrying thin slice 83 by roller 82 conveyances, and the slurry S of carrying on the thin slice 83, prolongs between carrying thin slice 83 that moves and scraping blade 84 and is shaped with required thickness.
The slurry S that is shaped, foaming groove 85 and the heating furnace 86 by carrying out heat treated successively by carrying thin slice 83 conveyances.In foaming groove 85, owing under high humility atmosphere, carry out heat treated, therefore can slurry S not cracked, make the blowing agent foaming.And, dry in heating furnace 86 as if the slurry S that forms the cavity because of foaming, then form and form the green single G of empty metal dust between particle by the state of organic bond joint.
Should green single G, after 83 separation of carrying thin slice, in not shown vacuum furnace, carry out degreasing, burn till, remove organic bond thus, can obtain the mutual sintering of each metal dust and become the foaming metal sintering thin slice (conductivity porous body) of three dimensional network ocular structure.
To cut off conductivity porous body and the dividing plate 122,152,162 that forms as mentioned above by formalizing shape, embed shaping as built in items, and can produce, possess the gas- diffusion electrode 11,51,61 that constitutes by the conductivity porous body and the gas diffusion layer member 10 of dividing plate 122,152,162 and resin frame 13,53,63 with one.
Below, the embedding of making gas diffusion layer member 10 with reference to figure 6 explanations is shaped.
At first, conductivity porous body (oxygen diffusion electrode 11,11) and dividing plate 122 are fixed as one by diffusion bond, and with it as built in items P.And, shown in Figure 44, in the die cavity 72 that forms between a pair of mould 70,71, arrange above-mentioned built in items P, and will be from the molten resin 75 of running channel 73 by cast gate 74 injections, be filled in the die cavity 72, thus the gas diffusion layer member 10 that gas-diffusion electrode 11, dividing plate 122 and resin frame 13 that formation is made of the conductivity porous body become one.
And, in Figure 44, utilized the gas-diffusion electrode 11 that forms catalyst layer 31 at surface element, but this catalyst layer 31 must not form on gas-diffusion electrode 11, also can on dielectric substrate 121, form, and,, then can also after embedding shaping, form if on gas-diffusion electrode 11, form.
In addition, gas diffusion layer member 50,60 also can be made by aforesaid embedding forming mode.
Promptly, with conductivity porous body (gas-diffusion electrode 51,61) and dividing plate 152,162, be fixed as one by diffusion bond, and with this as built in items, shown in Figure 44, in the die cavity 72 that forms between a pair of mould 70,71, arrange the conductivity porous body, and will be from the molten resin 75 of running channel 73 by cast gate 74 injections, be filled in the die cavity 72, thus the gas diffusion layer member 50,60 that gas- diffusion electrode 51,61, dividing plate 152,162 and resin frame 53,63 that formation is made of the conductivity porous body become one.
Owing to form resin frame 13,53,63 by above-mentioned embedding forming mode, therefore, gas- diffusion electrode 11,51,61 and resin frame 13,53,63, in the pore of gas- diffusion electrode 11,51,61 side mouth, molten resin is infiltrated to the degree of depth of about 5 μ m～1000 μ m harden, therefore can firmly engage.Connect each runner 10a, 10b, 10c, 10d, 50a, 50b, 50c, 50d, 60a, 60b, 60c, 60d or bolt insertion hole 10e, 50e, the 60e of resin frame,, can when above-mentioned reaction-injection moulding, form by the pin member 76 that is arranged at mould.
Embedding in the forming process, during the material selection polypropylene of resin frame 13,53,63, is 180 ℃, 80kN matched moulds with forming temperature, presses the 250kg/cm2 reaction-injection moulding to be shaped, and can obtain composite porous body 10,50,60.
In addition, formed gas diffusion layer member at 10,50,60 o'clock by embedding, die cavity 72 thickness when making mold closing (size of mould switch direction), a little littler than built in items P, and during mold closing between mould 70,71, make gas- diffusion electrode 11,51,61 compressions 3～90%, then gas- diffusion electrode 11,51,61 relative die cavitys 72 are fixed, can stop by the sprayed resin living position deviation of cutting down output, also can improve the evenness of gas- diffusion electrode 11,51,61.
In addition, if the hole diameter or the porosity of gas- diffusion electrode 11,51,61 are too small, then molten resin just can't infiltrate in the pore, thereby the grappling effect becomes inadequately, and can not fully obtain bond strength with resin frame 13,53,63, phenomenon can appear peeling off at the junction surface.On the other hand, if the hole diameter or the porosity are excessive, then owing to insufficient strength, the compression stress in the time of can't bearing ester moulding pressure and hardening of resin finally causes distortion.Thereby hole diameter is about 10 μ m～2mm, the porosity is about 40～98%, is advisable.
On the other hand, the material that forms the resin material of resin frame 13,53,63 can be selected thermoplastic resin, elastomer etc. for use, but to be the material of reaction-injection moulding get final product for it, can take into full account heat resisting temperature or hardness to this, and suitably selection gets final product.
And, each member of formation shown in the above-described embodiment, its all shapes or combination etc. are an example just, and in not breaking away from the scope of purport of the present invention, can carry out various changes according to designing requirement.In the above-mentioned execution mode, though the fuel cell with 4 groups of cell unit is illustrated, the present invention is not limited in 4 groups of cell unit, can be according to concrete needs, gas diffusion layer member 10 and dielectric substrate 121 are piled up, also can obtain high power fuel cell.
And, in the above-described embodiment, though fluid such as fuel or air, flowing out a pore by gas- diffusion electrode 11,51,61 from each runner emits, but if the porosity of gas- diffusion electrode 11,51,61 is lower or it is less to be communicated with pore, then runner will narrow down and elongated to the face direction, therefore, this can influence the smooth supply of fluid.At this moment, as shown in Figure 7, can form groove shape as the 3rd runner 142a, 142b on the two sides of dividing plate 142, and, if allow fluid in the 3rd runner 142a, 142b, to flow, then owing to the runner in the gas-diffusion electrode 11 shortens at thickness direction, therefore, do not press even do not improve supply, can promote the smooth supply of fluid yet.In addition, also pump can be set, press in order to the supply that improves fuel.
In addition, in the above-described embodiment, be provided with the gas diffusion layer member 10 of gas-diffusion electrode with the dividing plate two sides, formed a plurality of cells unit 131, but, can also will be only the gas diffusion layer member 50,60 of gas-diffusion electrode be set in one side, be attached to the dividing plate back side and use.
Embodiment 7
Figure 46 represents the use in solid polymer fuel cell cell member (plane battery unit member) 10 according to the embodiment of the invention 7 ".This plane battery unit member 10 " has: a dielectric substrate 121; The laminar conductivity porous body 11 of 4 couple (8) of clamping this dielectric substrate 121 and arranging; The resin frame 13 of surrounding around each of this conductivity porous body 11 and prolonging to the face direction; And be connected to each conductivity porous body 11 and the terminal of outside that is exposed at resin frame 13 with joint (terminal) 4.
In this plane battery unit member 10 " in; as clamping each conductivity porous body 11 fuel supplying (being methanol aqueous solution) that dielectric substrate 121 is arranged in the fuel electrodes of a side here; then ionization is taken place by catalyst reaction the hydrogen in the fuel; and mobile dielectric substrate 121; arrive as clamping each conductivity porous body 11 that dielectric substrate 121 is arranged in the air pole of opposite side, generate water by catalyst reaction and airborne oxygen reaction.On the other hand, the electronics that is produced by the ionization of hydrogen with being located at outside loop, by terminal 4, moves to air pole (conductivity porous body 11) from fuel electrodes (conductivity porous body 11).At this moment, by this movement of electrons, can produce above-mentioned electric energy.
Conduct hydrionic dielectric substrate 121, for example the polymer electrolytic film by fluororesin system forms.As being connected in electrode this dielectric substrate 121, that hold concurrently gas diffusion layers and collector body, be provided with conductivity porous body 11.
Conductivity porous body 11, in this polymer electrolyte fuel cell, be by having gas permeability and conductivity by the three dimensional network ocular structure, the sheet-like member of double thus gas diffusion layers and collector plate, particularly, for example with the thin slice of sintering metal powder, foaming metal sintering thin slice, metal nonwoven fabrics, folded net etc., according to the formation of want shape.
In conductivity porous body 11, be provided with catalyst layer 15 on surface towards dielectric substrate 121.This catalyst layer 15 (collector body) will comprise the polyelectrolyte solution that supports the atomic carbon particle of platinum series catalysts, coat the surface of conductivity porous body 11 and form.
In addition, if catalyst layer 15 get involved between dielectric substrate 121 and conductivity porous body 11.In the present embodiment, catalyst layer 15 is arranged at the surface portion of conductivity porous body 121, but also can forms at dielectric substrate 121 surface portions.
And, also be provided with the joint shape terminal 4 that is connected in this conductivity porous body 11.Terminal 4 is when being electrically connected the terminal for connecting of each conductivity porous body 11, can be used as the terminal of the male or female of fuel cell in two ends connected in series.In the present embodiment, form with thin metallic plate, and it is fixed in conductivity porous body 11 by modes such as spot welding, resistance welded, ultrasonic wave joints.
And, in this plane battery unit member 10 " in, because the electronics that generates in reaction on the catalyst layer 15 trickles in conductivity porous body 11 and terminal 4, therefore, conductivity porous body 11 and terminal 4 form with high conductive material.In addition, if corrosion phenomenon is when being a problem, utilize corrosion resistance material such as stainless steel to be advisable as these members (conductivity porous body 11, terminal 4).
These, dielectric substrate 121, each conductivity porous body 11 and terminal 4 are configured as one by resin frame 13.Resin frame 13 is filled between certain intervals conductivity porous body 11 side by side, and prolongs to the face direction of conductivity porous body 11.
When this resin frame 13 can be fixed as one dielectric substrate 121 and each conductivity porous body 11, but also between each conductivity porous body 11 of electric insulation and seal the side of conductivity porous body 11, thereby effectively stop the leakage of the air or the fuel (methyl alcohol) that are supplied in conductivity porous body 11.Therefore, resin frame 13 can select thermoplastic resin, elastomer (containing rubber) for use but etc. the material of reaction-injection moulding, only otherwise have conductivity and gas permeability get final product, therefore consider heat resisting temperature and hardness and suitably selection get final product.For example, if select soft resin for use, then can improve sealing.
In addition, for stoping fuel or the leakage of air phenomenon by conductivity porous body 11, be exposed to the terminal 4 of these resin frame 13 outsides (being the side in the present embodiment), also the material (being metal in the present embodiment) by no gas permeability forms.
In this resin frame 13, also bolt hole can be set, so that fix each member or fixed position.In addition, for further improving the sealing of periphery, the O ring can be set use groove, or utilize soft resin that protuberance is set.
As shown in figure 47, the plane battery unit member of Gou Chenging (use in solid polymer fuel cell cell member) 10 as mentioned above " in; be provided with: the conductivity porous body 11 that will clamp a side of dielectric substrate 121 utmost point that acts as a fuel; 11 of opposite side conductivity porous bodies are as air pole; with fuel electrodes and air pole wiring 16 Hes connected in series successively; by the porous matter 17A of portion that constitutes at felt of fuel electrodes fuel supplying etc.; the fuel supplies 17 by resin frame 17B covers can constitute polymer electrolyte fuel cell thus.
In addition, when hanging down,, can adopt following formation: as shown in figure 48, make terminal 4 outstanding respectively from the two ends of conductivity porous body 11 in order to improve its current collection effect as if the conductivity of conductivity porous body 11; Or as shown in figure 49, the big terminal 4 of contact-making surface with conductivity porous body 11 is set; Or it is as shown in figure 50, terminal 4 is prolonged along the length direction of conductivity porous body 11, and outstanding respectively or the like from two ends.
In addition, terminal 4 can expose at any one position on resin frame 13 surfaces, and for example, when integral body was all imbedded in the resin frame 13, the front end 4a that has terminal 4 only was exposed at the formation of the side 13a (Figure 51) of resin frame 13; Perhaps, only 13b exposes on resin frame 13, and side 13a does not then expose formations such as (Figure 52).In addition, can also adopt following formation, shown in Figure 53, whole terminal 4 be imbedded in the resin frame 13, and the through hole h that each terminal 4 connects resin frame 13 is set, expose the formation of terminal 4 at through hole h inner peripheral surface.
And, shown in Figure 54 and Figure 55,, then, therefore other terminals 4 need not be set in addition again because conductivity porous body 11 has the function of terminal if adopt the structure of direct connecting wiring at conductivity porous body 11.At this moment, in order to connect each conductivity porous body 11, can utilize: for example, will have the projection 18a that infiltrates in conductivity porous body 11, and each the conductivity porous body 11 that is positioned at adjacent battery unit subtend is with X-shaped shape interconnective " コ " word shape conductivity connecting elements 18 (Figure 54); Or have, insert near resin frame 13 parts two pairs of conductivity porous bodies 11 of adjacent two couple clamping part 19a and, conductivity clip 19 (Figure 55) connecting elements of the connecting portion 19b that prolongs to conductivity porous body 11 from this clamping part 19a.
The following describes plane battery unit member 10 according to the embodiment of the invention 7 " manufacture method.
This manufacture method is that as built in items, embedding is shaped with dielectric substrate 121, conductivity porous body 11 and terminal 4.
At first, shown in Figure 56, conductivity porous matter thin slice 11 ' the surface form catalyst layer 15.Catalyst layer 15 forms by following method, that is, for example will support the carbon dust of platinum and sneak in the polyelectrolyte solution that can form dielectric substrate 121, and conductivity porous matter thin slice 11 ' surface coated and form.And, coat conductivity porous matter thin slice 11 ' catalyst, tightly invest the open pores surface, and form the bigger catalyst layer 15 of surface area.
Then, shown in Figure 57, will be formed with the conductivity porous matter thin slice 11 of catalyst layer 15 ', after cutting off by institute's sizing, with it as conductivity porous body 11.And, shown in Figure 58, on each the conductivity porous body 11 after the cut-out, the terminal 4 that spot welding is made of sheet metal.
Shown in Figure 59, make 4 couple (8) the conductivity porous body 11 that is fixed with terminal 4 respectively, make catalyst layer 15 relatively to, and dielectric substrate 121 clamped, and with this as built in items, embed shaping.
Before embed being shaped, conductivity porous body 11 and dielectric substrate 121 are fixed by hot pressing mode, then can be easy to built in items is filled to the reaction-injection moulding mould.At this moment, by implementing hot press operation, dielectric substrate 121 is filled in the pore of the opening that is positioned at catalyst layer 15 surfaces, at this moment, can reduce the resistance between catalyst layer 15 and the dielectric substrate 121 thus because catalyst layer 15 contacts with large-area with dielectric substrate 121.And, reaction-injection moulding with mold heated to 100～120 ℃, with conductivity porous body 11 and the hot press of dielectric substrate 121 and the operation of resin reaction-injection moulding, can be implemented simultaneously.
The reaction-injection moulding that embeds shaping with the structure of mould is, shown in Figure 60, clamping built in items (dielectric substrate 121, conductivity porous body 11 and terminal 4) in the die cavity 72 that a pair of mould 70,71 forms, and utilize the pressure of sprayed resin, conductivity porous body 11 and dielectric substrate 121 in the die cavity are fixed, make it not removable, and carry out reaction-injection moulding.
, behind the filling built in items, in the die cavity 72 of mold closing, fill the molten resin 75 that sprays by cast gate 74 from running channel 73, thereby around each conductivity porous body 11, form resin frame 13 with in the mould at reaction-injection moulding.
Thereby, since with molten resin and conductivity porous body 11 with much at one thickness filling, therefore, a side major part of conductivity porous body 11 is exposed to plane battery unit member 10 " the surface.
And, when mold closing, make die cavity 72 thickness be slightly less than 3 layer thicknesses that constitute by conductivity porous body 11 and dielectric substrate 121, during mold closing between mould 70,71, make 11 compressions 3～90% of conductivity porous body, then, can more firmly built in items be fixed in the die cavity, also can improve the evenness of conductivity porous body 11 simultaneously for die cavity.
At this moment, because the surface of conductivity porous body 11 links to each other with template surface, so resin is with whole surface coverage, and just as exposing the surface formation resin frame 13 of conductivity porous body 11.
And, because in the pore of the side mouth of conductivity porous body 11, the infiltration thickness of molten resin reaches 5 μ m～1000 μ m and hardens, therefore can make conductivity porous body 11 and resin frame 13 firm joints (grappling effect), and the whole sidepiece of conductivity porous body 11 is covered by resin frame 13.
At this, for resin frame 13 outsides (side 13a, surperficial 13b) that are shaped, terminal 4 front ends need not be consistent, and promptly terminal 4 is outstanding also harmless from resin frame 13.And, because molten resin even cover the front end of terminal 4, when not exposing in resin frame 13 outsides thus,, front end is exposed gets final product by grind resin frame 13 etc.
And if the hole diameter of conductivity porous body 11 or the porosity are too small, then molten resin can not infiltrate in the pore, thereby air seal effect and grappling effect might become insufficient.In addition, if the hole diameter or the porosity are excessive,, can't bear that ester moulding is pressed and the compression during hardening of resin causes the possibility of being out of shape and have then because insufficient strength.Therefore, conductivity porous body 11, hole diameter are that the porosity is about 40～98%, is advisable about 10 μ m～2mm.
And, according to the cell member in the embodiment of the invention 7 10 ", also can adopt following method manufacturing.Here the manufacture method of mentioning is, from dielectric substrate 121 and pair of conductive porous body 11, constitute so-called film-electrode bond (MEA), again to the face direction side by side with a plurality of MEA, and with this as built in items, embed shaping.
That is, shown in Figure 61, with conductivity porous matter thin slice 11 ' by institute's sizing cut-out, at its surface coated catalyst, and formation has the conductivity porous body 11 of catalyst layer 15.Catalyst layer 15 generates by following method, that is, the carbon dust that supports platinum is sneaked in the polyelectrolyte solution that can form dielectric substrate 121, and form in the surface coated of conductivity porous body.And, coat the catalyst of conductivity porous body, by tightly investing the open pores surface, form the bigger catalyst layer 15 of surface area.
Shown in Figure 62, make the pair of conductive porous body 11 that is formed with catalyst layer 15, subtend catalyst layer 15 and being provided with, and dielectric substrate 121 is clamped, form film-electrode bond M by hot press again.
And, 4 couples of film-electrode bond M as built in items, are embedded shaping, produce the plane battery unit member 10 shown in Figure 63 thus " with 4 pairs of battery units (film-electrode bond M).Embed the shaping related content, identical with reference Figure 60 illustration.
In addition, in this plane battery unit member 10 " in, can utilize clip 19 shown in connecting elements shown in Figure 54 18 or Figure 55 etc., connect each conductivity porous body 11.
The following describes the foaming metal sintering method of producing sheet that is suitable for conductivity porous body 11.This foaming metal sintering thin slice 11 for example, burns till and makes the slurry S that contains metal dust be configured as thin shape and dry green single and make.
Slurry S is, for example (for example with metal dusts such as SUS316L, organic bond, methylcellulose or hydroxypropyl methylcellulose), solvent (water) mixes, in addition, also add as required, by the blowing agent of heat treated distillation or gasification (for example, carbon number be 5～8 water-insoluble hydrocarbon be organic solvent) organic solvent (for example, neopentane, hexane, heptane) or, defoamer (ethanol) etc.Figure 12 represents to make the green single manufacturing installation 80 of slurry S for thin shape by the shaping of scraping blade method.
Be green single manufacturing installation 80, at first, the feeding funnel 81 of slurry S arranged, supplies slurry S on by the carrying thin slice 82 of roller 83 conveyances from storage.The slurry S of carrying on the thin slice 82 prolongs between carrying thin slice 82 that moves and scraping blade 84 and is shaped with required thickness.
The slurry S that is shaped, foaming groove 85 and the heating furnace 86 by carrying out heat treated successively by carrying thin slice 82 conveyances.In foaming groove 85, owing under high humility atmosphere, carry out heat treated, therefore can slurry S not cracked, make the blowing agent foaming.And, dry in heating furnace 86 as if the slurry S that forms the cavity because of foaming, then form and form the green single G of empty metal dust between particle by the state of organic bond joint.
Should green single G, after separating from carrying thin slice 82, in not shown vacuum furnace, carry out degreasing, burn till, remove organic bond thus, can obtain the foaming metal sintering thin slice (conductivity porous body 11) of the mutual sintering of each metal dust.
And, utilize the formation of the polymer electrolyte fuel cell of cell member of the present invention, also have for example as described below.
Shown in Figure 64 and 65, for plane battery unit member 110 with fuel electrodes A and air pole B, if it is constituted: have porous matter portion 31 that preserves fuel supplying and the fuel supplies 30 that covers these resin frame 32, in the face direction side by side, then can control the thickness of whole fuel cell.
At this moment, because the conductivity porous body 112 of fuel electrodes A, become not porous matter portion 31 direct-connected structures with fuel supplies 30, therefore, shown in Figure 65 (in Figure 64), the through hole 113a to the perforation of face direction of resin frame 113 is set along the cross section target view that the a-a line is cut open.By this through hole 113a, the conductivity porous body 112 of porous matter portion 31 and fuel electrodes A is connected, and fuel supplying, the secondary product during discharging generating simultaneously, i.e. carbon dioxide gas.
And, shown in Figure 65, by install covering the tabular component 115 on fuel electrodes A side conductivity porous body 112 surfaces, and clog and the resin portion 32 of fuel supplies 30 between the gap, thereby can prevent from the fuel leak phenomenons to take place from fuel electrodes A conductivity porous body 112.Therefore, for example, can realize, above-mentioned tabular component 115 sides are arranged in the back side of LCD and are applicable to the structure of ultrathin notebook PC.
In addition, as the structure of connected porous matter portion 31 and fuel electrodes A conductivity porous body 112, shown in Figure 66, it is also passable that the groove 113b that prolongs to the face direction is set on the surface of resin frame 113.At this moment, if also also form the groove 115a that prolongs to the face direction on the surface of tabular component 115, make this groove 115a be communicated in 113 groove 113b and fuel electrodes A conductivity porous body 112 surfaces of resin frame, then, can pass through this groove 115a, than fuel electrodes A conductivity porous body 112 effective supply fuel more, the discharging carbon dioxide gas.
And, shown in Figure 67 and Figure 68, air pole B at cell member 110,210, when arranging as covering the members such as tabular component 116 on conductivity porous body 112,212 surfaces, for with air supply in conductivity porous body 112,212, can design following structure:, form the groove 116a (Figure 67) be communicated in conductivity porous body 112 on the surface of tabular component 116, or, form air vent hole 113a (Figure 68) etc. in the resin frame 113 of cell member 110.
The invention provides a kind ofly, can guarantee effective usable floor area of composite porous body, can improve the composite porous body and the manufacture method thereof of its operability again.
And the structural design that becomes one by resin frame of a plurality of conductivity porous bodies side by side in the plane is very easy to the gas diffusion layer member in the present invention, also can realize so-called plane battery unit easily.
Moreover, the invention provides a kind ofly, can shorten the packing engineering of fuel cell with conductivity porous body, can improve the gas diffusion layer member and the manufacture method thereof of the polymer electrolyte fuel cell of its assembling precision again.
In addition, realization along with the high strength gas diffusion layer member, cut down the quantity of parts and improved operability, thereby also reduced the possibility of fuel leak, thereby can produce simple in structure, small volume and less weight and the high high performance fuel cell of productivity.
Claims (20)
1. a composite porous body is characterized in that, form as one with the laminar conductivity porous body of three dimensional network ocular structure with to the resin portion that the face direction of this conductivity porous body prolongs,
And, a plurality of described conductivity porous bodies are arranged side by side, and around these a plurality of described conductivity porous bodies, are provided with described resin portion.
2. composite porous body as claimed in claim 1 is characterized in that, contains inorganic filler in described resin portion.
3. composite porous body as claimed in claim 2 is characterized in that, described inorganic filler is fibrous, and the content in described resin portion is below the above 60wt% of 5wt% of this resin portion simultaneously.
4. the gas diffusion layer member of a polymer electrolyte fuel cell is by constituting as each described composite porous body in the claim 1～3.
5. the gas diffusion layer member of polymer electrolyte fuel cell as claimed in claim 4 is characterized in that, described resin portion is to surround described conductivity porous body resin frame on every side.
6. the gas diffusion layer member of polymer electrolyte fuel cell as claimed in claim 5 is characterized in that, be provided with from the outstanding terminal joint of described conductivity porous body, and this terminal is exposed to the outside of described resin frame with joint.
7. the gas diffusion layer member of polymer electrolyte fuel cell as claimed in claim 4 is characterized in that, has: the oxygen diffusion electrode, with the one side of described conductivity porous body as oxygen supply face, another side as electrode surface; Resin portion along the face direction of oxygen diffusion electrode is extended is made of the non-conductive material that is arranged at two sides in the described oxygen diffusion electrode sidepiece at least; Clathrate frame portion, it is arranged at oxygen supply face side, is connected with described resin portion of extending along the face direction of oxygen diffusion electrode, and has the peristome that makes described oxygen supply open towards the outside.
8. the gas diffusion layer member of polymer electrolyte fuel cell as claimed in claim 7, it is characterized in that, described oxygen diffusion electrode is provided with to cut apart a plurality of modes, and is provided with by the connection box that non-conductive material constituted that connects between each oxygen diffusion electrode.
9. as the gas diffusion layer member of claim 7 or polymer electrolyte fuel cell as claimed in claim 8, it is characterized in that described clathrate frame portion is made of non-conductive material.
10. as the gas diffusion layer member of claim 7 or polymer electrolyte fuel cell as claimed in claim 8, it is characterized in that, described clathrate frame portion is made of conductive material, and is provided with to cut apart a plurality of modes corresponding to a plurality of described oxygen diffusion electrodes.
11. the gas diffusion layer member as claim 4 or polymer electrolyte fuel cell as claimed in claim 5 is characterized in that, the collector body with the two-dimensional mesh ocular structure that prolongs to the face direction is set on described conductivity porous body surface.
12. the gas diffusion layer member of polymer electrolyte fuel cell as claimed in claim 11 is characterized in that, described collector body, and it has at least a part to infiltrate in the surface of described conductivity porous body.
13. a use in solid polymer fuel cell cell member is characterized in that having: the dielectric substrate that constitutes by solid macromolecule electrolyte; At least one pair of conductivity porous body is clamped dielectric substrate, gets involved catalyst layer between described conductivity porous body and described dielectric substrate; With surround this conductivity porous body around and the resin frame that prolongs to the face direction,
Wherein, have manyly side by side, and manyly be provided with described resin frame around to described conductivity porous body at this to described conductivity porous body.
14. use in solid polymer fuel cell cell member as claimed in claim 13 is characterized in that, described resin frame is set up in the mode on every side of surrounding described conductivity porous body and described dielectric substrate.
15. the manufacture method of a composite porous body, it is characterized in that: this method is used for producing as each described composite porous body of claim 1～3, specifically: with described conductivity porous body as built in items, according to embedding shaping with the edge ways of connecting sprayed resin of this conductivity porous body.
16. the manufacture method of the gas diffusion layer member of a polymer electrolyte fuel cell, it is characterized in that: with the conductivity porous body as built in items, according to embedding shaping, produce as claim 4 or gas diffusion layer member as claimed in claim 5 with the edge ways of connecting sprayed resin of this conductivity porous body.
17. the manufacture method of the gas diffusion layer member of a polymer electrolyte fuel cell, it is characterized in that: resin portion and clathrate frame portion that this method is used to produce extending along the face direction of oxygen diffusion electrode carry out the gas diffusion layer member as claimed in claim 7 that integral type forms, specifically: with described conductivity porous body as built in items, by edge and oxygen supply face sprayed resin, produce resin portion that described face direction along the oxygen diffusion electrode is extended and described clathrate frame portion carries out the gas diffusion layer member as claimed in claim 7 that integral type forms to described conductivity porous body.
18. manufacture method as the gas diffusion layer member of claim 11 or polymer electrolyte fuel cell as claimed in claim 12, it is characterized in that: will on the surface of described conductivity porous body, arrange described collector body and the laminated body that forms as built in items, utilize these die face fixing this built in items that is arranged on the die face towards the thickness direction compression of described laminated body, form the matched moulds operation of die cavity simultaneously, after treating that this matched moulds operation finishes, spray molten resin to described die cavity, on the outer peripheral edges of described laminated body, form the resin portion that prolongs towards the face direction thus along whole edge integral type.
19. the manufacture method of a use in solid polymer fuel cell cell member, it is characterized in that: this method is used for producing as each described cell member of claim 13～14, described method is: with described dielectric substrate and at least one pair of conductivity porous body as built in items, according to carrying out sprayed resin and the embedding forming process of the described resin frame that is shaped with the edge ways of connecting of described conductivity porous body, wherein said at least one pair of conductivity porous body is clamped described dielectric substrate, gets involved catalyst layer between described conductivity porous body and described dielectric substrate.
20. use in solid polymer fuel cell cell member manufacture method as claimed in claim 19, it is characterized in that: for described dielectric substrate and described conductivity porous body, when under the state of getting involved described catalyst layer each other, embedding shaping, implement hot press.
Applications Claiming Priority (22)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003-133239 | 2003-05-12 | ||
| JP2003133239 | 2003-05-12 | ||
| JP2003147633A JP2004349198A (en) | 2003-05-26 | 2003-05-26 | Gas diffusion layer member for fuel cell of solid polymer type, and its manufacturing method |
| JP2003-147633 | 2003-05-26 | ||
| JP2003-173266 | 2003-06-18 | ||
| JP2003173266A JP4524544B2 (en) | 2003-05-12 | 2003-06-18 | Composite metal porous body and method for producing the same |
| JP2003173265A JP2005011624A (en) | 2003-06-18 | 2003-06-18 | Cell member for solid polymer fuel battery and manufacturing method of the same |
| JP2003-173265 | 2003-06-18 | ||
| JP2003176363A JP4682500B2 (en) | 2003-06-20 | 2003-06-20 | GAS DIFFUSION LAYER MEMBER FOR SOLID POLYMER FUEL CELL AND METHOD FOR PRODUCING GAS DIFFUSION LAYER MEMBER |
| JP2003-176363 | 2003-06-20 | ||
| JP2003-188135 | 2003-06-30 | ||
| JP2003188135A JP4400111B2 (en) | 2003-06-30 | 2003-06-30 | Composite carbonaceous porous body and method for producing the same |
| JP2003195937A JP4887597B2 (en) | 2003-07-11 | 2003-07-11 | Solid polymer fuel cell, gas diffusion layer member and method for producing the same |
| JP2003-195937 | 2003-07-11 | ||
| JP2003-195938 | 2003-07-11 | ||
| JP2003195938A JP4686961B2 (en) | 2003-07-11 | 2003-07-11 | Polymer electrolyte fuel cell, gas diffusion layer member for polymer electrolyte fuel cell, and method for producing the same |
| JP2003428308 | 2003-12-24 | ||
| JP2003-428307 | 2003-12-24 | ||
| JP2003428307A JP2005190745A (en) | 2003-12-24 | 2003-12-24 | Member for gas diffusion layer of solid polymer fuel cell, and its manufacturing method |
| JP2003-428308 | 2003-12-24 | ||
| JP2004-107788 | 2004-03-31 | ||
| JP2004-121670 | 2004-04-16 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800127276A Division CN1788378B (en) | 2003-05-12 | 2004-05-07 | Composite porous body, member for gas diffusion layer, cell member, and their manufacturing methods |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101281969A CN101281969A (en) | 2008-10-08 |
| CN101281969B true CN101281969B (en) | 2011-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100967118A Expired - Fee Related CN101281969B (en) | 2003-05-12 | 2004-05-07 | Composite porous body, gas diffusion layer member, cell member, and manufacturing method thereof |
| CN2004800127276A Expired - Fee Related CN1788378B (en) | 2003-05-12 | 2004-05-07 | Composite porous body, member for gas diffusion layer, cell member, and their manufacturing methods |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800127276A Expired - Fee Related CN1788378B (en) | 2003-05-12 | 2004-05-07 | Composite porous body, member for gas diffusion layer, cell member, and their manufacturing methods |
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| CN (2) | CN101281969B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009145090A1 (en) * | 2008-05-26 | 2009-12-03 | アクアフェアリー株式会社 | Fuel cell and method of manufacture thereof |
| JP5613902B2 (en) * | 2010-11-10 | 2014-10-29 | 三菱マテリアル株式会社 | Porous implant material |
| CN103117401B (en) * | 2011-11-17 | 2015-07-08 | 旭化成电子材料株式会社 | Polyelectrolyte laminated membrane |
| JP6644445B2 (en) * | 2015-09-17 | 2020-02-12 | フィガロ技研株式会社 | Electrochemical gas sensor |
| WO2017068914A1 (en) * | 2015-10-23 | 2017-04-27 | セイコーエプソン株式会社 | Electrode assembly manufacturing method, electrode assembly, and battery |
| CN107604379A (en) * | 2017-09-25 | 2018-01-19 | 浙江高成绿能科技有限公司 | A kind of SPE membrane electrodes and its preparation technology |
| US10783805B2 (en) * | 2018-01-15 | 2020-09-22 | LaserSharp FlexPak Services, LLC | Microchannel device for controlling gas, vapor, pressure within a package |
| JP7020284B2 (en) * | 2018-05-14 | 2022-02-16 | トヨタ自動車株式会社 | Jig for joining |
| CN110181781A (en) * | 2019-06-10 | 2019-08-30 | 江苏博联硕焊接技术有限公司 | A kind of conformal cooling mold and its processing method |
| CN110556550A (en) * | 2019-08-01 | 2019-12-10 | 武汉中极氢能产业创新中心有限公司 | Flow field plate and air-cooled electric pile |
| CN110690455A (en) * | 2019-11-05 | 2020-01-14 | 陶霖密 | Proton exchange membrane fuel cell, stack and method for manufacturing the same |
| JP7466299B2 (en) * | 2019-12-12 | 2024-04-12 | 株式会社エフ・シー・シー | Fuel Cell Systems |
| JP7257346B2 (en) * | 2020-02-25 | 2023-04-13 | 株式会社ニフコ | Mesh for insert molding |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416184A (en) * | 2001-11-01 | 2003-05-07 | 哈尔滨工业大学 | Metal compound bipolar plate of fuel cell with proton exchange film |
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2004
- 2004-05-07 CN CN2008100967118A patent/CN101281969B/en not_active Expired - Fee Related
- 2004-05-07 CN CN2004800127276A patent/CN1788378B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416184A (en) * | 2001-11-01 | 2003-05-07 | 哈尔滨工业大学 | Metal compound bipolar plate of fuel cell with proton exchange film |
Non-Patent Citations (2)
| Title |
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| JP平10-199551A 1998.07.31 |
| JP昭58-5976A 1983.01.13 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1788378B (en) | 2010-07-14 |
| CN101281969A (en) | 2008-10-08 |
| CN1788378A (en) | 2006-06-14 |
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