WO2001003214A1 - Separateur de pile a combustible a polymere solide, son procede de fabrication et pile combustible ainsi obtenue - Google Patents

Separateur de pile a combustible a polymere solide, son procede de fabrication et pile combustible ainsi obtenue Download PDF

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Publication number
WO2001003214A1
WO2001003214A1 PCT/JP2000/004098 JP0004098W WO0103214A1 WO 2001003214 A1 WO2001003214 A1 WO 2001003214A1 JP 0004098 W JP0004098 W JP 0004098W WO 0103214 A1 WO0103214 A1 WO 0103214A1
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WO
WIPO (PCT)
Prior art keywords
separator
fuel cell
conductive
ribs
polymer electrolyte
Prior art date
Application number
PCT/JP2000/004098
Other languages
English (en)
Japanese (ja)
Inventor
Hideki Kato
Yasunori Morio
Original Assignee
Ibiden Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ibiden Co., Ltd. filed Critical Ibiden Co., Ltd.
Publication of WO2001003214A1 publication Critical patent/WO2001003214A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
    • 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

Definitions

  • the present invention relates to a polymer electrolyte fuel cell, a separator thereof, and a method for producing the separator.
  • PEFC polymer electrolyte fuel cells
  • This type of fuel cell has a membrane / electrode stack (single cell).
  • the membrane / electrode laminate (single cell) is, for example, a solid polymer membrane (hereinafter referred to as a proton exchange membrane), which is one of proton exchange ion exchange membranes as an electrolyte layer, and is disposed on both sides of the membrane And a pair of electrodes.
  • a solid polymer membrane has a hydrogen ion exchange group in a molecule constituting the membrane and can be in a saturated water-containing state, thereby functioning as an ion conductive electrolyte.
  • Each electrode supports a metal catalyst such as platinum.
  • One electrode is called the hydrogen electrode (cathode) and the other is the oxygen electrode (anode).
  • a pair of separators is arranged on both sides of the membrane / electrode laminate. The outer edges of both electrodes and the ion exchange membrane are supported between a pair of separators.
  • a separator material a molded article mainly composed of carbon powder and a thermosetting resin has been proposed.
  • Hydrogen gas (H 2 ) is supplied to the hydrogen electrode via the separator on the hydrogen electrode side. Due to the catalytic reaction at the hydrogen electrode, hydrogen gas is dissociated into hydrogen ions (H +) and electrons (e —). The hydrogen ions pass through the proton exchange membrane and move toward the oxygen electrode, and the electrons move through an external circuit to the oxygen electrode.
  • the oxygen electrode oxygen gas (0 2) is supplied. Therefore, at the oxygen electrode, the oxygen gas reacts with the hydrogen ions and the electrons passing through the external circuit by a catalytic reaction to produce water (H 2 ⁇ ). At this time, the electrons passing through the external circuit form a current and can supply power to the load. In other words, an electromotive force is obtained by the reverse reaction of the electrolysis reaction using oxygen gas and hydrogen gas as fuel.
  • a conventional separator is made of gas impermeable carbon (for example, glassy carbon or resin-impregnated carbon material), and is provided with a large number of ribs on one or both sides as convex portions. Each rib is arranged so that its upper surface contacts the electrode. Fluids such as oxygen gas, hydrogen gas, and moisture flow through the region formed between the ribs.
  • gas impermeable carbon for example, glassy carbon or resin-impregnated carbon material
  • An object of the present invention is to provide a relatively inexpensive and highly accurate separator and a polymer electrolyte fuel cell. Another object of the present invention is to provide a method for producing the above separator.
  • a first aspect of the present invention is directed to a solid comprising a base material, and a plurality of conductive protrusions arranged on at least one surface of the base material at predetermined intervals.
  • a separator for a polymer fuel cell Provided is a separator for a polymer fuel cell.
  • a fluid passage is formed between adjacent convex portions. It is preferable that the base material has conductivity, and each of the protrusions is a rib printed on the base material using a conductive material.
  • the base material is an insulating base material having first and second surfaces, and the plurality of protrusions are formed of a first plurality of ribs and a first plurality of ribs respectively printed on the first and second surfaces using a conductive material.
  • the plurality of ribs wherein the base material includes a plurality of conductive portions for electrically connecting each first rib on the first surface and each second rib on the second surface. Is preferred. It is preferable that the conductive portion has an opening formed in the first and second surfaces, and the opening is covered by the rib.
  • the substrate is preferably a laminate including a first insulating substrate, a second insulating substrate, and a conductive layer disposed between the first and second insulating substrates.
  • the first insulating base material includes a first plurality of ribs formed on the surface thereof by printing a conductive material, and a first plurality of conductive portions electrically connected to the first plurality of ribs. Is preferred.
  • the second insulating base includes a second plurality of ribs formed on the surface thereof by printing a conductive material and a second plurality of conductive portions electrically connected to the second plurality of ribs. It is preferred.
  • the conductive layer electrically connects the first plurality of conductive portions and the second plurality of conductive portions.
  • Each conductive portion is filled with a conductive material, and each conductive portion preferably has an inner wall surface on which a texture is formed.
  • Each conductive portion is a through hole filled with a conductive material, and the plated through hole preferably has a textured inner wall surface.
  • Each conductive portion is a through hole filled with an insulating resin material, and the through hole preferably has an inner wall surface on which a texture is formed.
  • the conductive material has high purity and the impurity concentration in the conductive material is relatively low.
  • the conductive material preferably contains a carbon paste.
  • the substrate is preferably a sheet molded body containing carbon powder.
  • the insulating base is preferably a printed wiring board base.
  • a polymer electrolyte fuel cell comprising: a proton exchange membrane; a pair of electrodes disposed on both surfaces of the proton exchange membrane; and the separator disposed on each of the electrodes.
  • a third aspect of the present invention provides a method for producing a separator for a polymer electrolyte fuel cell.
  • the method includes a step of forming a molded body mainly composed of carbon, and a step of forming a plurality of convex portions having a predetermined shape by printing a conductive material on the surface of the molded body.
  • FIG. 1 is an exploded perspective view of a polymer electrolyte fuel cell according to a first embodiment of the present invention.
  • FIG. 2 is a schematic sectional view of the fuel cell of FIG.
  • FIG. 3 is a schematic view showing the procedure for manufacturing the fuel cell of FIG.
  • FIG. 4 (a) to 4 (d) are schematic cross-sectional views illustrating a method of manufacturing the fuel cell of FIG.
  • Figure 5 is a schematic diagram of a fuel cell during discharge.
  • FIG. 6 is a partially exploded perspective view of a separator of a polymer electrolyte fuel cell according to a second embodiment of the present invention.
  • FIG. 7 is a schematic sectional view of the fuel cell of FIG.
  • FIG. 9 is a partially exploded perspective view of a separator of a polymer electrolyte fuel cell according to a third embodiment of the present invention.
  • FIG. 10 is a schematic sectional view of the fuel cell of FIG.
  • 11 (a) to 11 (d) are schematic cross-sectional views illustrating a method for manufacturing a separator according to a fourth embodiment of the present invention.
  • FIG. 12 (a) is a schematic sectional view of a separator according to a fifth embodiment of the present invention.
  • Fig. 12 (b) Partial enlarged cross-sectional view of the inner wall surface of the fitted through hole.
  • FIG. 13 is a schematic sectional view of a separator according to a sixth embodiment of the present invention.
  • the fuel cell 1 includes a membrane / electrode laminate L 1 and a separator 2.
  • the membrane 'electrode laminate L1 has a proton exchange membrane 3 and a pair of electrodes (hydrogen electrode 4A, oxygen electrode 4B) attached to both sides of the proton exchange membrane 3.
  • the proton exchange membrane 3 allows the passage of hydrogen ions.
  • the material of the proton exchange membrane 3 is preferably perfluorocarbonsulfonic acid.
  • the hydrogen electrode 4A and the oxygen electrode 4B are air-permeable mat-like materials mainly composed of carbon fiber or the like, and are preferably formed in a rectangular shape. In this mat-like material, platinum and palladium are supported as catalysts.
  • the mat-like material may be added with a water-repellent fluororesin or the like.
  • the thick flange portion 3 a is provided on the outer edge of the proton exchange membrane 3.
  • a pair of separators 2 are arranged on both sides of the membrane electrode stack L1.
  • Separator 2 is formed in a rectangular plate shape that is slightly larger than hydrogen electrode 4A and oxygen electrode 4B.
  • the flange portion 3a is sandwiched by the outer edges of both separators 2 via a rubber packing 5 as a sealing member.
  • the rubber packing 5 prevents fluid leakage from between the flange portion 3a and the separator 2 to the outside.
  • the separator 2 includes a fluid-impermeable conductive substrate 11 and a plurality of ribs 12 as convex portions formed on both surfaces of the conductive substrate 11.
  • the term fluid impermeable as used herein represents the nature of the material is m 2 ⁇ s ec transmittance N 1 X 1 0- 4 ⁇ 1 X 1 CT 12 cc of H e gas.
  • a plate-like molded body 15 mainly composed of carbon powder and a thermosetting resin is used (see FIG. 3).
  • a plate-like molded body 15 can be obtained by, for example, a known extrusion molding method, a sheet molding method, a roll molding method, a doctor blade method, or the like.
  • the role of the carbon powder in the plate-like molded body 15 is to reduce the electrical resistivity and improve the conductivity of the separator 2.
  • Usable carbon powders include natural graphite powder, artificial graphite powder, glassy carbon, mesocarbon, carbon black and the like. Mixtures of these can also be used. In this case, it is desirable to use high-purity carbon powder with as low an impurity content as possible. Specifically, the impurity concentration is 200 p ⁇ ⁇ ! About 300 ppm of flaky carbon powder is added to the plate-like molded body 15.
  • thermosetting resin in the plate-like molded body 15 The role of the thermosetting resin in the plate-like molded body 15 is to provide the separator 2 (particularly, the conductive substrate 11) with a property of impervious to a fluid such as gas, and to provide a suitable sheet formability.
  • examples of usable thermosetting resins include epoxy resin, polyimide resin, and phenol resin. Of these, phenolic resins are particularly preferred. This is because fuanol resin is excellent in moldability and fluid impermeability, and is also excellent in acid resistance, heat resistance, and cost.
  • the phenolic resins include novolak resins and resole resins. Mixtures of novolak phenolic resins and resol phenolic resins can also be used.
  • the plurality of ribs 12 have the same cross-sectional shape, and are formed parallel to each other in a surface region excluding the outer edge of the conductive base material 11.
  • the membrane / electrode laminate L 1 When the membrane / electrode laminate L 1 is placed between the two separators 2, the upper end surface of each rib 1 2 abuts on the proton exchange membrane 3, and as a result, a groove-shaped area (fluid passage) 13 is adjacent
  • the ribs 12 are formed between the ribs. Fluids such as oxygen gas, hydrogen gas, and water move along the fluid passage 13.
  • the height of rib 1 2 is 1! It is set to about 500 / m. More preferable height is ⁇ ⁇ ⁇ ⁇ ⁇ ! About 300 ⁇ . If the ribs 12 are too high, the thickness of the entire separator 2 increases, and the size of the fuel cell stack may be increased. If the ribs 12 are too low, the cross-sectional area of the fluid passage 13 becomes small, and the fluid may not flow smoothly.
  • the width of the rib 12 is set to about 1 ⁇ to about 100 ⁇ m. A more preferred width is about 100 ⁇ m to 700 ⁇ m. If the width of ribs 1 and 2 is too large, the fluid passage
  • the ribs 12 are formed by attaching a conductive material such as a conductive paste to both surfaces of the conductive substrate 11.
  • the ribs 12 of the first embodiment are formed by printing a carbon paste P1 mainly containing carbon powder as conductive particles.
  • the first reason for selecting carbon paste P1 is that carbon has no danger of poisoning the proton exchange membrane 3 by elution of cations unlike metals.
  • the second reason is that if the ribs 12 are made of carbon, the difference in thermal expansion coefficient between the ribs 12 and the conductive base material 11 containing carbon powder as a main component is almost the same, and the ribs 12 and the conductive base materials 11 The reason for this is that the bonding strength with the aluminum alloy also increases.
  • a carbon powder and a thermosetting resin are blended in a predetermined ratio to obtain a mixture.
  • This mixture is adjusted to an appropriate viscosity by adding a solvent such as methanol, and kneaded well using a kneader.
  • a solvent such as methanol
  • acetone or high-viscosity higher alcohols may be used.
  • the flake-like mixture is pulverized with a mixer or the like to use as a raw material for sheet molding.
  • a plate-like molded body 15 having a thickness of about 1 mm to 10 mm is continuously molded from the obtained raw material by molding using an extruded sheet molding machine 14.
  • the formed plate-like molded body 15 is conveyed continuously to the next step.
  • the plate-like molded body 15 is continuously compressed using a press machine 16.
  • the plate-like molded body 15 After pressing, the plate-like molded body 15 which has been tightened to some extent is further heated at a predetermined temperature for a predetermined time. Specifically, the plate-like molded body 15 is heated at 150 ° C. to 250 ° C. for 5 minutes to 30 minutes using a known curing device 17. as a result However, the plate-shaped molded body 15 loses its flexibility and hardens.
  • the printing step is performed according to the following procedure.
  • carbon paste P1 (trade name "Dorite", manufactured by Fujikura Kasei Co., Ltd.) was used and its viscosity was adjusted to 200 O cps before printing.
  • the amount of carbon in paste P1 is about 65% by weight. Note that a dispersant, a leveling agent, and the like are added to the carbon paste P1.
  • the plate-shaped molded body 15 of FIG. 4A is conveyed to the printing machine 18.
  • a predetermined metal mask 19 is brought into close contact with the plate-like molded body 15.
  • the metal mask 19 has a plurality of elongated openings 19a.
  • the carbon paste P1 is placed on the metal mask 19, and the roller squeegee 20 is moved in a predetermined direction as shown in FIG. 4 (c).
  • carbon paste P1 is imprinted on the opening 19a of the metal mask 19.
  • a rib 12 having a predetermined height and a predetermined width is printed on the plate-like molded body 15.
  • the printing process may be performed on one side at a time or on both sides simultaneously.
  • the metal mask 19 is peeled off from the conductive base material 11 (FIG. 4D).
  • the ribs 12 may be printed by a screen printing method using a screen printing machine.
  • the plate-like molded body 15 is conveyed to the cutting machine 21 and cut into a predetermined length.
  • the plate-like molded body 15 may be punched into a predetermined shape by a punching press.
  • the fuel cell 1 is completed by assembling the separator 2 thus manufactured together with the membrane / electrode laminate L1 and the rubber packing 5. In order to obtain a sufficiently large electromotive force, about ten to about several hundred fuel cells 1 may be stacked to form a fuel cell stack. Next, the power generation mechanism of the fuel cell 1 will be described with reference to FIG.
  • a load such as a motor, that is, an external circuit is electrically connected between the hydrogen electrode 4A and the oxygen electrode 4B.
  • the hydrogen electrode 4 A side separator The hydrogen gas is continuously supplied from the radiator 2 together with the moisture. The moisture and the hydrogen gas flow in a certain direction along the fluid passage 13 on the hydrogen electrode 4A side.
  • oxygen gas is continuously supplied together with moisture from the separator 2 on the oxygen electrode 4B side. The moisture and oxygen gas flow in a certain direction along the fluid passage 13 on the oxygen electrode 4B side.
  • the hydrogen gas supplied to the hydrogen electrode 4 A side generates hydrogen ions by a catalytic reaction at the hydrogen electrode 4 A.
  • the generated hydrogen ions move toward the oxygen electrode 4 B while passing through the proton exchange membrane 3.
  • the hydrogen ions that have reached the oxygen electrode 4 B react with oxygen gas by a catalytic reaction at the oxygen electrode 4 B to generate water.
  • electrons move from the hydrogen electrode 4 A to the oxygen electrode 4 B through an external circuit. That is, a current flows from the oxygen electrode 4B to the hydrogen electrode 4A, and an electromotive force is obtained.
  • a DC current flows through the external circuit, and a load such as a motor is driven. According to the first embodiment, the following effects can be obtained.
  • the separator 2 Since the fluid does not pass through the conductive base material 11, the fluid can be flown along the fluid passage 13 without fail. Therefore, according to the fuel cell 1 using the separator 2, a stable electromotive force can be obtained. In addition, since the expensive press-molding mold and long-time machining are not required in the rib 12 forming process, the separator 2 is manufactured relatively inexpensively, and the manufacturing cost of the fuel cell 1 is reduced.
  • the substrate 11 has conductivity, the ribs 12 formed on both surfaces thereof are electrically connected to each other. Therefore, by stacking the separators 2, the fuel cell stack can be configured relatively easily.
  • the ribs 12 formed by printing carbon paste P1 which is a conductive material, have higher precision and fineness than expensive press-molding dies and ribs formed by long-time machining. is there.
  • the separator 2 having the high-precision and fine ribs 12 can be manufactured inexpensively and reliably without the need for expensive press molding dies or long-time machining. And it can be manufactured efficiently.
  • members common or similar to those of the first embodiment will be denoted by the same reference numerals, and differences will be mainly described.
  • an insulating base material 35 is used as the base material of the separator 31.
  • Suitable examples of the insulating substrate 35 include general substrates for printed wiring boards such as a glass epoxy substrate, a polyimide substrate, a polyester substrate, and a fluororesin substrate. This type of insulating base material 35 has the advantage of being excellent in heat resistance and insulating properties.
  • a plurality of ribs 12 are printed as convex portions.
  • the rib 12 has conductivity, and a noble metal paste P2 containing at least one noble metal selected from gold, silver, platinum, palladium and the like is used as the material.
  • the reason why the noble metal paste P2 was selected is that the noble metal has a low ionization tendency, so that even if the metal comes into contact with the proton exchange membrane 3, the proton exchange membrane 3 is hardly poisoned.
  • the insulating base material 35 is provided with a plated through hole 32 as a conductive portion.
  • the plated through hole 32 is opened in the insulating base material 35 corresponding to the bottom of the rib 12, and a land is formed around the opening of the plated through hole 32. Therefore, the ribs 12 on both surfaces of the insulating base material 35 are electrically connected to each other.
  • the opening diameter of the plating through hole 32 is set slightly smaller than the width of the rib 12. Accordingly, since the ribs 12 cover the openings of the through holes 32, the fluid flowing in the fluid passages 13 is prevented from contacting or entering the plated through holes 32. It is preferable to fill the plating through hole 32 with a conductive material.
  • the conductive material may be the noble metal paste P2 or any other substance.
  • an insulating base material 35 as a starting material is prepared.
  • the insulating base material 35 may be one that has already been cut to a predetermined length, or one that has been wound into a roll. If a roll-shaped material is selected, a step of separating the material into a predetermined length later is required.
  • a hole 33 is formed at a predetermined position of the insulating base material 35.
  • a mask (not shown) is provided on the insulating base material 35, a catalyst nucleus is provided, the catalyst nucleus is activated, and electroless copper plating is performed.
  • FIG. 8 (c) the inner wall of the hole 33 and the periphery (land) of the opening are attached, and a plated through hole 32 is formed.
  • a printing process is performed.
  • a silver paste manufactured by Fujikura Kasei Co., Ltd., trade name: "Do One Tit" was used and its viscosity was adjusted to 2000 cps before printing.
  • a dispersant, an antifoaming agent and the like are added to the silver paste.
  • a metal mask 19 is brought into close contact with the insulating base material 35 conveyed to the printing press.
  • the noble metal paste P2 is placed on the metal mask 19, and the roller squeegee 20 is moved in a predetermined direction.
  • the noble metal paste P2 is imprinted on the opening 19a of the metal mask 19, and the rib 12 having a predetermined height and a predetermined width is printed.
  • the metal mask 19 is peeled off from the insulating base material 35 (see Fig. 8 (e)). Note that screen printing by a screen printing machine may be performed without using the metal mask 19.
  • the desired separator 31 is completed by the above series of steps.
  • the separator 31 is assembled together with the membrane / electrode laminate L1 and the rubber packing 5, the fuel cell 1 shown in FIG. 7 is completed. According to the second embodiment, the following effects can be obtained.
  • the ribs 12 formed by printing the noble metal paste P2 have the advantage that they are more accurate and finer than the ribs formed by press molding dies or long-time machining.
  • the separator 41 of the third embodiment employs a laminated structure.
  • the separator 41 is composed of a first insulating base material 35 A, a second insulating base material 35 B, and a layered conductor 42 arranged between the two insulating base materials 35 A and 35 B. It is a laminated body.
  • the insulating base materials 35A and 35B the general printed wiring board base material described in the second embodiment is used.
  • the layered conductor 42 for example, a conductive metal plating layer represented by a copper plating layer, an aluminum plating layer, a gold plating layer, or the like is used.
  • a sputtered layer of a conductive metal, a printed layer of a conductive metal paste, a foil made of a conductive metal, or the like may be used.
  • the thickness of the conductor 42 is preferably set to about 1 ⁇ m to 100 ⁇ m, and particularly preferably about 10 / xm to 100 ⁇ m. If the conductor 42 is too thin, the electrical resistance will increase, causing heat generation. Conversely, if the conductor 42 is too thick, the problem of an increase in electrical resistance does not occur, but the overall thickness of the separator 41 increases. Therefore, when the fuel cell stack is configured, there is a possibility that the fuel cell stack becomes large and the weight increases.
  • the conductor 42 is preferably formed one size smaller than the outer dimensions of both insulating bases 35A and 35B. Another good thing is that the conductor
  • a plurality of first ribs 12A are formed on one surface of the first insulating base material 35A by printing a noble metal paste P2.
  • the first insulating base material 35A is provided with a through hole 32A.
  • the plated through hole 32 A opens at the position corresponding to the first rib 12 A of the first insulating base material 35 A, and the plating around the opening of the plated through hole 32 A is the first rib 1 Electrically connected to 2 A.
  • a plurality of second ribs 12B are formed on one surface of the second insulating base material 35B by printing the noble metal paste P2.
  • the first rib 12A and the second rib 12B are orthogonal to each other.
  • a through-horn 32B is provided on the second insulating substrate 35B.
  • the plated through hole 3 2 B is opened at a position corresponding to the second rib 12 B of the second insulating base material 35 B, and the plated portion around the opening of the plated through hole 3 2 B is connected to the second rib 12 B. Electrically connected.
  • the first insulating base material 35 A plated through hole 32 A and the second insulating base material 35 B plated through hole 32 B are electrically connected to each other via a conductor 42. And You. That is, the ribs 12 A on the front surface and the ribs 12 B on the back surface of the laminate are electrically connected by the plated through holes 32 A, 32 B and the conductor 42 (interlayer connection).
  • the separator 51 is manufactured by the procedure shown in FIGS. 11 (a) to 11 (d).
  • the conducting portion 52 may be in the form of a hole (ie, a through hole) or a groove (ie, a through groove).
  • Set the insulating base material 35 on the printing machine make a metal mask 19 adhere to the insulating base material 35, print the noble metal paste P2, which is a conductive material, with a roller squeegee 20, and remove the ribs 12 Form.
  • the viscosity and the like of the noble metal paste P2 are appropriately set so that the noble metal paste P2 is filled in the conductive portion 52.
  • the ribs 12 on the front surface and the back surface of the insulating base material 35 are electrically connected by the noble metal paste P2 filled in the conductive portion 52.
  • the carbon paste P1 of the first embodiment can be used instead of the noble metal paste P2. According to the fourth embodiment, the following effects can be obtained.
  • a through hole 32 is formed in the separator 61 as a conductive part.
  • An electroless copper plating layer 62 as a plating layer is formed on the inner wall surface of the plating through hole 32.
  • a texture layer 63 having fine projections is formed on the plating layer 62. That is, the plating layer 62 has a rough surface 63.
  • the texture layer 63 is also formed on the surface of the land 64 of the plating hole 32. In order to obtain a sufficient anchor effect, it is preferable that the surface roughness Ra of the texture layer 63 is set to 1 ⁇ m to 20 ⁇ m.
  • the texture layer 63 is a needle-like alloy layer obtained by electroless copper one-ply monophosphate plating or the like.
  • a blackened layer obtained by oxidizing copper, a blackened reduced layer obtained by oxidizing and reducing copper, and a brown reduced layer may be selected.
  • a needle-like alloy layer is desirable. The reason is that the needle-shaped alloy layer has, for example, the following favorable properties. 1) Good contact with the filled material. 2) Because it is tough, it is hard and hard to crack. 3) Excellent heat cycle characteristics.
  • An example of the composition of an electroless copper plating bath for forming a needle-like alloy layer is shown below. Copper sulfate::! ⁇ 40 g Z liter,
  • Nickel sulphate 0:! To 6.0 Og / liter,
  • hypophosphite 100-: 100 g / liter
  • Surfactant 0.01-1; 10 g / l.
  • the thickness of the texture layer 63 that is, the distance from the smooth conductor surface on the inner wall of the plated through hole to the top of the needle-shaped alloy (the distance between the tip of the projection and the bottom) is 0.5 ⁇ ! Set to ⁇ 7.0 m. Preferably, it is 1.0 ⁇ to 5.0 // m, and more preferably, 1.5 ⁇ ! Within the range of ⁇ 3.0 m. If the texture layer 63 is too thick, the plating process takes a long time, and the production cost increases. In addition, the protrusions of the texture layer 63 become brittle, and a gap is easily generated between the texture layer 63 and the filling material. On the other hand, if the texture layer 63 is too thin, the anchor effect becomes insufficient, and a gap tends to be formed between the texture layer and the filling material.
  • the texture layer 63 is desirably protected by a tin layer.
  • the reasons are listed below. 1)
  • the alloy plating is easily dissolved in an acid or an oxidizing agent. Therefore, if the plating of the alloy is protected by the tin layer, the dissolution of the plating of the alloy is prevented, and the well-formed projections of the texture layer 63 are maintained. 2)
  • the tin layer can prevent the generation of voids between the texture layer 63 and the filling material, and can improve the adhesion.
  • Tin is an industrially inexpensive and less toxic metal. 4) Since tin is a metal precipitated by a substitution reaction with copper, tin can be coated without destroying the needle-shaped alloy of the copper-nickel-phosphorus layer.
  • examples of the filling material for the plated through hole 32 include a resin insulating material and a conductive material.
  • the resin insulating material it is preferable to use a matrix resin containing a filler.
  • a filler When such a filler is contained, the thermal expansion coefficient of the filler material is reduced, and the heat cycle characteristics are improved.
  • the matrix resin include an epoxy resin, a polyimide resin, and a polyether sulfone resin. Among these, it is desirable to use an epoxy resin.
  • an organic filler such as an epoxy resin or a polyimide resin, or an inorganic filler such as silica or alumina can be used.
  • the average particle size of the filler is 0.1 l / im to 10 im Desirably. If the average particle diameter is too small, it is difficult to obtain the effect of relaxing expansion and contraction during curing.
  • the filler becomes larger than the protrusions of the texture layer 63, and there is a possibility that the ability to follow the filler and the texture layer 63 (ease of conformity) may be deteriorated.
  • a noble metal paste P2 for forming a rib containing at least one noble metal selected from gold, silver, platinum, palladium and the like is used.
  • a paste containing a base metal such as copper can be used instead of the noble metal.
  • the carbon paste P1 of the first embodiment can be used instead of the paste containing metal.
  • the adhesion of the filling material to the electroless copper plating layer 62 by the anchor effect of the texture layer 63 Is improved. Further, since there is no void in the plated through hole 32, the heat cycle characteristics are improved, and cracks are less likely to occur near the plated through hole 32. As a result, it is possible to provide a separator 61 having excellent reliability and a fuel cell 1 having excellent reliability.
  • the separator 71 of the sixth embodiment has a structure in which the inner wall surface of the conductive portion 52 and the insulating base material 35 A texture layer 72 having fine projections is formed on the back surface.
  • the texture layer 72 is formed, for example, as follows. First, the conductive portion 52 is formed. The following resin material is applied to the insulating base material 35. Then, the layer of the resin material is roughened by the oxidation treatment.
  • the resin material heat-resistant resin fine particles (filament resin) which are soluble in an acid or an oxidizing agent and which have been cured in advance, and which are cured by an acid or an oxidizing agent, And a heat-resistant resin liquid (matrix resin) which becomes hardly soluble.
  • the matrix resin may be a photosensitive resin or a thermosetting resin.
  • the heat-resistant resin particles include: 1) Condensation of heat-resistant resin powder with an average particle size of 2 ⁇ m or less, and an average particle size of 2 ⁇ II! Agglomerated particles having a size of ⁇ 10 m, 2) a particle mixture of a heat-resistant resin powder having an average particle size of 2 ⁇ m to 10 // m and a heat-resistant resin powder having an average particle size of 2 ⁇ m or less, 3) Average particle size 2 ⁇ IT! Pseudo particles formed by adhering a heat-resistant resin powder having an average particle diameter of 2 m or less or an inorganic fine powder to the surface of a heat-resistant resin powder having a thickness of up to 10 ⁇ m.
  • the particle mixture of 2) is particularly preferable. When the texture layer 72 is formed by roughening the particle mixture, a more reliable anchor effect can be secured.
  • the heat-resistant resin fine particles serving as the filler resin for example, a powder of an epoxy resin, a polyester resin, a bismaleimid triazine resin, or the like can be used.
  • the size of the resin fine particles is desirably in the range of 0.1 / xm to 10 ⁇ .
  • Epoxy resins, epoxy-modified polyimide resins, polyimide resins, and funor resins can be used as the heat-resistant resin to be the matrix resin. Further, photosensitivity may be imparted to these resins.
  • a varnish in which the resin fine particles are uniformly dispersed can be obtained by mixing a predetermined amount of the above resin fine particles with the liquid of these heat-resistant resins, adding a solvent such as butylcellsolve, and stirring.
  • This varnish is uniformly applied to the insulating substrate 35. At this time, not only the front and back surfaces of the insulating base material 35 but also the inner wall surface of the conductive portion 52 is covered with the varnish. After that, a hardening process is performed. D. A resin layer (not shown) is formed.
  • the oxidizing agent used in the oxidation treatment examples include chromic acid, chromate, permanganate, and ozone.
  • an oxidation treatment is performed using such an oxidizing agent, only the filler resin portion is selectively dissolved, and countless fine textures as anchors are formed on the matrix resin surface. That is, the surface of the resin layer is roughened, and the texture layer 72 is formed. It is desirable that the surface roughness (R max) of the texture layer 72 be set in the range of 1 // m to 20 / z m. This is because a suitable anchor effect can be obtained when the content is within this range. According to the sixth embodiment, the following effects can be obtained.
  • the texture layer 72 may be formed directly on the inner wall surface of the conductive portion 52 without forming the resin layer on the inner wall surface of the conductive portion 52.
  • the form may be changed as follows.
  • the layout of the ribs 12, 12A, and 12B can be arbitrarily changed. Also, for example, a projection may be formed instead of the elongated ribs 12, 12 A, and 12 B.
  • the pressing step and the curing step may be omitted.
  • the carbon paste P1 of the first embodiment and the noble metal paste P2 of the second embodiment urethane-based, rubber-based, and elastomer-based inks can be used as the conductive material for printing. .
  • the conductive substrate is not limited to the plate-like molded body 15
  • thermoplastic resin film obtained by carbonizing by a heat treatment or the like, A little.
  • the ribs 12, 12 A, and 12 B as the convex portions may be formed by another method such as a coating method, a plating method, and a sticking method.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne un séparateur (2, 31, 41, 51, 61) à prix relativement modéré, une pile à combustible à polymère solide de précision (1) comprenant un substrat (11) et des nervures (12). Ces dernières sont ménagées par impression d'une matière conductrice (P1) sur les deux côtés du substrat. Des passages pour fluide (13) sont délimités entre les nervures adjacentes et traversés par le gaz d'hydrogène et le gaz d'oxygène.
PCT/JP2000/004098 1999-07-02 2000-06-22 Separateur de pile a combustible a polymere solide, son procede de fabrication et pile combustible ainsi obtenue WO2001003214A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP18900599 1999-07-02
JP11/189005 1999-07-02
JP2000165980A JP3530462B2 (ja) 1999-07-02 2000-06-02 固体高分子型燃料電池のセパレータ及び固体高分子型燃料電池
JP2000/165980 2000-06-02

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Publication Number Publication Date
WO2001003214A1 true WO2001003214A1 (fr) 2001-01-11

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WO (1) WO2001003214A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6869718B2 (en) * 2000-11-09 2005-03-22 Sanyo Electric Co., Ltd. Separator used for fuel cell, method for manufacturing the separator, and the fuel cell
KR20170077174A (ko) * 2014-12-19 2017-07-05 니폰 제온 가부시키가이샤 도전성 잉크
US10383519B2 (en) 2014-10-21 2019-08-20 uBiome, Inc. Method and system for microbiome-derived characterization, diagnostics and therapeutics for conditions associated with functional features

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Publication number Priority date Publication date Assignee Title
JP2002343374A (ja) * 2001-05-18 2002-11-29 Mitsubishi Pencil Co Ltd 燃料電池用セパレータ及びその製造方法
JP4031740B2 (ja) 2003-07-15 2008-01-09 日東電工株式会社 燃料電池用セパレータ及びそれを用いた燃料電池
US7306874B2 (en) * 2003-11-20 2007-12-11 General Motors Corporation PEM fuel cell stack with coated flow distribution network
WO2005057699A1 (fr) 2003-12-09 2005-06-23 Nitta Corporation Separateur et procede de production d'un separateur
KR100545992B1 (ko) 2004-03-10 2006-01-25 (주)퓨얼셀 파워 연료전지용 분리판 및 제조방법, 그리고 이러한 분리판을포함하는 연료전지 스택
KR100529080B1 (ko) * 2004-03-25 2005-11-15 삼성에스디아이 주식회사 연료 전지 시스템 및 이에 사용되는 스택
JP2012226868A (ja) * 2011-04-15 2012-11-15 Toyota Motor Corp 燃料電池用セパレータおよびその製造方法
KR101343223B1 (ko) 2012-03-22 2013-12-18 삼성전기주식회사 연료 전지용 분리판 및 그 제조방법
KR101574268B1 (ko) * 2013-03-25 2015-12-04 한국에너지기술연구원 편향기 일체형 분리막
KR101445166B1 (ko) 2013-03-28 2014-10-06 한국에너지기술연구원 편향기 일체형 분리막 제조방법
TWI538287B (zh) * 2015-06-04 2016-06-11 Taiwan Carbon Nano Technology Corp Reduce the contact resistance of the electrochemical cell

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04149966A (ja) * 1990-10-15 1992-05-22 Ishikawajima Harima Heavy Ind Co Ltd 固体電解質型燃料電池
JPH0536425A (ja) * 1991-02-12 1993-02-12 Tokyo Electric Power Co Inc:The 固体電解質型燃料電池用合金セパレータ及びその製造 方法
JPH07272731A (ja) * 1994-03-29 1995-10-20 Mazda Motor Corp 燃料電池スタック構造
JPH08273696A (ja) * 1995-03-29 1996-10-18 Mazda Motor Corp 燃料電池スタック構造
WO1997050138A1 (fr) * 1996-06-25 1997-12-31 E.I. Du Pont De Nemours And Company Electrolyseur a membranes en polymere avec plaque bipolaire de type a moulages protuberants en polymere
JP2000133282A (ja) * 1998-10-21 2000-05-12 Ishikawajima Harima Heavy Ind Co Ltd 固体高分子電解質型燃料電池用セパレータ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04149966A (ja) * 1990-10-15 1992-05-22 Ishikawajima Harima Heavy Ind Co Ltd 固体電解質型燃料電池
JPH0536425A (ja) * 1991-02-12 1993-02-12 Tokyo Electric Power Co Inc:The 固体電解質型燃料電池用合金セパレータ及びその製造 方法
JPH07272731A (ja) * 1994-03-29 1995-10-20 Mazda Motor Corp 燃料電池スタック構造
JPH08273696A (ja) * 1995-03-29 1996-10-18 Mazda Motor Corp 燃料電池スタック構造
WO1997050138A1 (fr) * 1996-06-25 1997-12-31 E.I. Du Pont De Nemours And Company Electrolyseur a membranes en polymere avec plaque bipolaire de type a moulages protuberants en polymere
JP2000133282A (ja) * 1998-10-21 2000-05-12 Ishikawajima Harima Heavy Ind Co Ltd 固体高分子電解質型燃料電池用セパレータ

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6869718B2 (en) * 2000-11-09 2005-03-22 Sanyo Electric Co., Ltd. Separator used for fuel cell, method for manufacturing the separator, and the fuel cell
US10383519B2 (en) 2014-10-21 2019-08-20 uBiome, Inc. Method and system for microbiome-derived characterization, diagnostics and therapeutics for conditions associated with functional features
KR20170077174A (ko) * 2014-12-19 2017-07-05 니폰 제온 가부시키가이샤 도전성 잉크
CN107004870A (zh) * 2014-12-19 2017-08-01 日本瑞翁株式会社 导电性油墨
EP3236525A4 (fr) * 2014-12-19 2018-05-30 Zeon Corporation Encre conductrice
US10263261B2 (en) 2014-12-19 2019-04-16 Zeon Corporation Electrically conductive ink

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