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WO2007102469A1 - Pile a combustible - Google Patents

Pile a combustible Download PDF

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Publication number
WO2007102469A1
WO2007102469A1 PCT/JP2007/054199 JP2007054199W WO2007102469A1 WO 2007102469 A1 WO2007102469 A1 WO 2007102469A1 JP 2007054199 W JP2007054199 W JP 2007054199W WO 2007102469 A1 WO2007102469 A1 WO 2007102469A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
fuel
fuel cell
electrode
membrane
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2007/054199
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English (en)
Japanese (ja)
Inventor
Jun Momma
Yoshihiko Nakano
Kazuhiro Yasuda
Naoya Hayamizu
Takashi Kawakubo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Original Assignee
Toshiba Corp
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
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Priority to JP2008503847A priority Critical patent/JPWO2007102469A1/ja
Publication of WO2007102469A1 publication Critical patent/WO2007102469A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1055—Inorganic layers on the polymer electrolytes, e.g. inorganic coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1076—Micromachining techniques, e.g. masking, etching steps or photolithography
    • 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 small fuel cell.
  • lithium ion secondary batteries In response to such a demand for secondary batteries, for example, lithium ion secondary batteries have been developed.
  • the operation time of portable electronic devices tends to increase further, and in lithium ion secondary batteries, the improvement in energy density is almost limited from the viewpoints of materials and structures. It is becoming impossible to cope with.
  • DMFC methanol is oxidized and decomposed at the fuel electrode to generate carbon dioxide, protons and electrons.
  • the air electrode water is generated by oxygen obtained from air, protons supplied from the fuel electrode through the electrolyte membrane, and electrons supplied from the fuel electrode through an external circuit. In addition, power is supplied by electrons passing through this external circuit.
  • the membrane when the membrane is thinned, the strength of the porous substrate is lowered, and the swelling of the electrolyte itself cannot be suppressed. Moreover, when the elastic modulus of the electrolyte is low, it is difficult to maintain the strength as the electrolyte membrane. If the electrolyte membrane is damaged, the fuel cell cannot be operated.
  • the object of the present invention is to suppress fuel permeation to the oxidant electrode through the electrolyte membrane without causing problems such as breakage of the electrolyte membrane or reduced adhesion to the electrode, and as a result, the output characteristics are improved. It is to provide an improved fuel cell.
  • a fuel cell according to the present invention is a fuel cell comprising a fuel electrode, an oxidant electrode, and an electrolyte membrane disposed between the fuel electrode and the oxidant electrode,
  • the electrolyte membrane includes a porous base material, a first electrolyte filled in pores of the porous base material, and a second electrolyte that covers a surface of the porous base material.
  • the electrolyte has a higher elastic modulus than the second electrolyte.
  • FIG. 1 is a perspective view of an electrolyte membrane for a direct methanol fuel cell according to an embodiment of the present invention.
  • FIG. 2 is a perspective view showing a porous substrate used for the electrolyte membrane of FIG. 1.
  • FIG. 3 shows an electrolyte membrane for a direct methanol fuel cell and a fuel electrode according to an embodiment of the present invention. It is sectional drawing of the electric power generation element which consists of an air electrode.
  • FIG. 4 is a schematic cross-sectional view showing a direct methanol fuel cell of Example 1.
  • a fuel cell of the present invention includes a porous substrate, a first electrolyte filled in the porous substrate, and a porous substrate as an electrolyte membrane.
  • An electrolyte membrane comprising a second electrolyte formed on the surface is used.
  • the second electrolyte is characterized by having a lower elastic modulus (Young's modulus) than the first electrolyte.
  • the porous electrolyte is filled with the first electrolyte having a high elastic modulus, the swelling of the electrolyte can be suppressed, and the fuel moves to the oxidant electrode through the electrolyte membrane. (Methanol crossover) can be suppressed. At the same time, sufficient strength can be maintained even if the thickness of the porous substrate is reduced, and damage to the electrolyte membrane can be prevented.
  • the second electrolyte having a low elastic modulus covers the surface of the porous substrate, the electrolyte membrane can be brought into close contact with the catalyst layer supported on the gas diffusion layer, thereby realizing low resistance. The power to do S.
  • FIG. 1 schematically shows a perspective view of an electrolyte membrane for a direct methanol fuel cell according to an embodiment of the present invention.
  • FIG. 2 is a perspective view showing a porous substrate used for the electrolyte membrane of FIG.
  • the electrolyte membrane 5 includes a porous base material 1 and layered second electrolytes 2a and 2b (hereinafter referred to as a second electrolyte layer) formed on the surface of the porous base material 1.
  • the porous substrate 1 has a plurality of through holes 3 penetrating from one reaction surface la to the other reaction surface lb.
  • the through hole 3 is filled with a first electrolyte 4.
  • the second electrolyte layer 2a having a lower elastic modulus than the first electrolyte 4 covers the reaction surface la of the porous substrate 1 so as to be in contact with the first electrolyte 4 filled in the through-holes 3. .
  • the second electrolyte layer 2b having a lower elasticity than the first electrolyte 4 covers the reaction surface lb of the porous substrate 1 so as to be in contact with the first electrolyte 4 filled in the through holes 3. is doing. In this way, the first electrolyte layer 2a, 2b is filled with the through-hole 3 of the porous substrate 1 connecting only the surface of the porous substrate 1. By contacting with 4, the proton conductivity of the electrolyte membrane can be improved.
  • porous substrate having a large number of precision-processed through-holes for the porous substrate 1 described above.
  • a Si substrate porous body made by MEMS (micro electro mechanical system) technology can be considered.
  • the porous substrate 1 desirably has rigidity.
  • a metal silicon substrate having a hole location precisely designed by lithography and then a precise and fine through-hole formed by etching can be exemplified.
  • the diameter of the hole is in the range of 0.1 .mu.m lOOOO zm, preferably 1 .mu.m to 100 .mu.m, more preferably 5 zm to 30 zm.
  • a substrate material any rigid material that can be precisely processed can be used for metal, ceramic, glass, and resin.
  • the metal material include silicon, stainless steel, and titanium, and aluminum may be used as long as the electrolyte to be inserted is glass.
  • the ceramic examples include oxide ceramics such as alumina, silica, and zirconium, nitride ceramics such as silicon nitride, and carbide ceramics such as silicon carbide. An oxynitride such as sialon can also be used.
  • ceramics are polycrystalline, but single crystals may also be used.
  • a sapphire substrate can be considered.
  • glass when glass is used, its fracture toughness becomes a problem, so the size may be limited.
  • quartz glass or the like can be considered.
  • the resin material a highly rigid engineering plastic material is desirable.
  • polyether ether ketone for example, PEEK (registered trademark) of Victorex
  • PEEK registered trademark of Victorex
  • the thermal conductivity of the porous substrate is preferably 1 W / mk or more.
  • the thickness of the porous substrate is preferably in the range of 10 to 500 zm. A more preferred range is 20 to: 100 x m.
  • the first electrolyte 4 inserted into such a porous substrate includes inorganic materials such as tungstic acid and phosphotungstic acid as materials having a large elastic modulus.
  • inorganic gas For lath phosphate glass and the like are conceivable.
  • organic materials such as hydrocarbon resins having sulfonic acid groups (polystyrene sulfonic acid, polyether ketone sulfonic acid, etc.) are conceivable. However, it is not limited to these.
  • a fluororesin having a sulfonic acid group such as a perfluorosulfonic acid polymer (naphtho ion (duo Bonn brand name, registered trademark), Flemion (brand name, manufactured by Asahi Glass Co., Ltd.), etc.
  • a perfluorosulfonic acid polymer naphtho ion (duo Bonn brand name, registered trademark), Flemion (brand name, manufactured by Asahi Glass Co., Ltd.), etc.
  • naphtho ion dueo Bonn brand name, registered trademark
  • Flemion brand name, manufactured by Asahi Glass Co., Ltd.
  • an organic electrolyte is used for the first electrolyte 4 and an organic polymer electrolyte is used for the second electrolytes 2a and 2b.
  • an organic electrolyte is used for the first electrolyte 4 and an organic polymer electrolyte is used for the second electrolytes 2a and 2b.
  • inorganic electrolytes inorganic electrolytes containing phosphorus are desirable. This is considered to be because the formed phosphate ion structure effectively acts on proton conductivity.
  • FIG. 3 shows a cross-sectional view of an MEA in which a catalyst layer and a gas diffusion layer are adhered to such an electrolyte membrane.
  • An air electrode (oxidant electrode) and a fuel electrode are arranged with the electrolyte membrane 5 interposed therebetween.
  • the fuel electrode includes a fuel electrode catalyst layer 6 laminated on one surface of the electrolyte membrane 5 and a fuel electrode gas diffusion layer 7 laminated on the fuel electrode catalyst layer 6.
  • the anode gas diffusion layer 7 serves to uniformly supply fuel to the anode catalyst layer 6 and also serves as a current collector for the anode catalyst layer 6.
  • the air electrode includes an air electrode catalyst layer 8 stacked on the opposite surface of the electrolyte membrane 5 and an air electrode gas diffusion layer 9 stacked on the air electrode catalyst layer 8.
  • the air electrode gas diffusion layer 9 serves to uniformly supply oxygen as an oxidant to the air electrode catalyst layer 8 and also serves as a current collector for the air electrode catalyst layer 8.
  • the fuel electrode gas diffusion layer 7 is laminated with a fuel electrode conductive layer (not shown), and the air electrode gas diffusion layer 9 is laminated with an air electrode conductive layer (not shown).
  • the fuel electrode conductive layer and the air electrode conductive layer are composed of a porous layer such as a mesh made of a conductive metal material such as gold.
  • Such an MEA is installed in a fuel cell and generates electric power by supplying fuel and air.
  • Fuel cells can be broadly divided from the form of the fuel, and the fuel consisting of methanol aqueous solution is supplied to the fuel electrode of the MEA while being adjusted with a pump so that the amount is constant.
  • An active fuel cell that uses a pump to supply air to the MEA air electrode and a natural supply of vaporized methanol to the MEA, while external air is also supplied to the air electrode.
  • There are passive fuel cells that are not equipped with extra equipment such as pumps.
  • the electrolyte membrane according to the present invention can be used for any of them, and the use thereof is not limited.
  • the fuel that can be used in the present invention is not limited to methanol.
  • fuel that can be used in a fuel cell such as ethanol, propanolol, glycolole, dimethyl ether, formic acid, and an aqueous solution containing at least one of these compounds. If so, it is not particularly limited.
  • the direct methanol fuel cell shown in Fig. 4 was produced as follows.
  • An electrolyte membrane was formed. First, in order to produce a precisely processed rigid porous membrane, the following processing was performed using a silicon substrate as a material.
  • a silicon substrate having a diameter of 6 inches is used, and a perforated plate having a region on which a through hole having a diameter of 10 mm and a diameter of 10 / im is present at an opening area ratio of 55% in a 20 mm square region by lithography.
  • the resist-coated silicon substrate was exposed by lithography and developed to obtain a silicon substrate having a pattern transferred as designed. This silicon substrate was dry-etched by the Bosch etching method using SF and CF gases as decomposition gases. Etching silicon with SF with
  • Etching holes were formed to a depth of 100 ⁇ m or more over 1 hour. Residual resist on the surface is removed by ashing the resulting silicon substrate, Further, polishing was performed from the back surface by CMP (Chemical Mechanical Polishing) to obtain a porous body having a thickness of 50 / m. This porous membrane was cut along a 20 mm region to obtain a porous body for an electrolyte membrane. Thereafter, the porous body was heat-treated in air at 800 ° C. to form an oxide film on the surface as an electric insulating layer.
  • CMP Chemical Mechanical Polishing
  • this porous body was filled with a calcium phosphate glass gel produced by the Zonore gel method by a reduced pressure suction method. After filling, the gel was heated to 400 ° C in an electric furnace in an air atmosphere to convert the gel into electrolyte glass. On the other hand, a sampler for measuring the mechanical properties of the electrolyte glass was prepared and the elastic modulus was measured. As a result, it became clear that the elastic modulus was 60 to 70 GPa.
  • the porous membrane filled with the electrolyte glass (first electrolyte) is carefully polished to remove only the electrolyte glass adhering to the surface, and the oxide layer on the silicon substrate surface is sufficiently removed. In the state of leaving, both sides were smooth.
  • a DE2020: Nafion (registered trademark) solution manufactured by Dupont was applied to both surfaces of the smooth surface, and a Nafion layer having an average thickness of about 10 ⁇ m was disposed on the surface of the perforated plate as a second electrolyte layer.
  • the elastic modulus of the Nafion layer is 0.2 to 0.3 GPa, and it is clear that the elastic modulus is smaller than that of the electrolyte glass.
  • the elastic modulus of the first electrolyte and the second electrolyte in the present invention is determined by analyzing each electrolyte and specifying its specific component to determine the specific elastic modulus of each electrolyte, and from the determined elastic modulus. It is possible to compare the two.
  • the electrolyte membrane in which the through-hole 3 of the porous body 1 is filled with the first electrolyte 4 having a high elastic modulus and the surface thereof is coated with the second electrolytes 2a and 2b having a low elastic modulus. 5 was obtained.
  • the second electrolytes 2 a and 2 b were in contact with the first electrolyte 4 filled in the through holes 3 of the porous body 1.
  • platinum-supported graphite particles were mixed with DE2020 manufactured by Dupont and a homogenizer to produce a slurry, which was applied to a carbon paper as the air electrode gas diffusion layer 9. Then, this was dried at room temperature to produce an air electrode in which the air electrode gas diffusion layer 9 was laminated with the air electrode catalyst layer 8. Furthermore, carbon particles carrying platinum ruthenium alloy particles were mixed with Dupoint DE2020 and a homogenizer to prepare a slurry, which was applied to the carbon paper as the fuel electrode gas diffusion layer 7. Then, this is dried at room temperature, and the fuel electrode gas diffusion layer 7 A fuel electrode was prepared by laminating a fuel electrode catalyst layer 6 on the substrate.
  • the electrolyte membrane 5 was sandwiched between an air electrode and a fuel electrode, and pressed under the conditions of a temperature of 120 ° C. and a pressure of 10 kgf / cm 2 , thereby producing a membrane electrode assembly (MEA) 10.
  • MEA membrane electrode assembly
  • the membrane electrode assembly 10 was sandwiched between gold foils having a plurality of openings for taking in air and vaporized methanol, thereby forming the air electrode conductive layer 11 and the fuel electrode conductive layer 12.
  • the air electrode conductive layer 11 and the fuel electrode conductive layer 12 may be made of, for example, a porous layer (for example, a mesh) or a foil body made of a metal material such as gold or nickel, instead of the gold foil having a plurality of holes, or stainless steel.
  • a composite material in which a conductive metal material such as steel (SUS) is coated with a highly conductive metal such as gold can be used.
  • a laminate in which the membrane electrode assembly (MEA) 10, the fuel electrode conductive layer 12, and the air electrode conductive layer 11 described above were laminated was sandwiched between two frames 13a and 13b made of resin.
  • a rubber O-ring 14 is interposed between the air electrode side of the membrane electrode assembly 10 and the one frame 13a, and between the fuel electrode side of the membrane electrode assembly 10 and the other frame 13b. And sealed.
  • the fuel electrode side frame 13b was fixed to the liquid fuel tank 16 via a gas-liquid separation membrane 15 with screws.
  • a gas-liquid separation membrane 15 for the gas-liquid separation membrane 15, a 0.1 mm thick silicone sheet was used.
  • a porous plate was disposed on the frame 13a on the air electrode side, and a moisture retaining layer 17 was formed.
  • a cover 19 is formed by placing a stainless steel plate (SUS304) with a thickness of 2mm on which air inlets 18 (diameter 2.5mm, number 8) for air intake are formed. And fixed by screwing.
  • a fuel cell was produced in the same manner as in Example 1 except that the thickness of the silicon substrate was 100 ⁇ m, and the voltage in the open circuit state and the maximum value of the output were measured from the current value and the voltage value.
  • the maximum surface temperature of the fuel cell was measured with a thermocouple attached to the surface of the cover. Table 1 shows the measurement results.
  • a fuel cell was prepared in the same manner as in Example 1 except that the thickness of the silicon substrate was 20 ⁇ m, and the voltage in the open circuit state and the maximum value of the output were measured from the current value and the voltage value.
  • the maximum surface temperature of the fuel cell was measured with a thermocouple attached to the surface of the cover. Table 1 shows the measurement results.
  • the structure of the electrolyte membrane used in Comparative Example 1 is exactly the same as in Example 1.
  • the force that the Si porous substrate is filled with the electrolyte glass On the other hand, both sides are covered with the electrolyte glass, and the organic electrolyte is completely The structure is not applied.
  • the obtained electrolyte membrane was sandwiched between an air electrode and a fuel electrode manufactured in the same manner as in Example 1, pressed at a temperature of 120 ° C and a pressure of 10 kgf / cm 2 , and membrane electrode joining was performed.
  • a body (MEA) was prepared. At this point, cracks occurred in the inorganic electrolyte glass on the electrolyte membrane surface.
  • the membrane / electrode assembly was subjected to a plurality of processes for taking in air and vaporized methanol.
  • the fuel electrode conductive layer and the air electrode conductive layer were formed by sandwiching with gold foil having an opening. Furthermore, it was sandwiched between two resin frames while fixing the state as it was.
  • Sealing is performed by interposing a rubber O-ring between the air electrode side of the membrane electrode assembly and one frame, and between the fuel electrode side of the membrane electrode assembly and the other frame. did. Subsequently, the frame on the fuel electrode side was fixed to the liquid fuel tank with screws through a gas-liquid separation membrane. A 0.1 mm thick silicone sheet was used for the gas-liquid separation membrane. On the other hand, a porous plate was placed on the air electrode side frame to form a moisture retention layer. A stainless steel plate (SUS304) having the same configuration as that described in Example 1 was placed on the moisturizing layer to form a cover, and the entire cover was fixed by screws.
  • Example 1 As in Example 1, 5 ml of pure methanol was injected into the liquid fuel tank of the fuel cell prototyped as described above, and the voltage in an open circuit state at a temperature of 25 ° C and a relative humidity of 50%. And out The maximum force was measured from the current and voltage values. The maximum value of the surface temperature of the fuel cell was measured with a thermocouple attached to the cover surface. Table 1 shows the measurement results.
  • the configuration of the electrolyte membrane used in Comparative Example 2 is as follows. In other words, a porous material having the same structure as in Example 1 was prepared, and a calcium phosphate glass gel prepared by the sol-gel method described in Example 1 was formed on one side with a thickness of 50 ⁇ m. Then, the film was heated to 400 ° C. to obtain a porous plate having a phosphate glass film on one surface. This perforated plate was vacuum impregnated with Dupoint's DE2020: Nafion (registered trademark) solution several times from the side opposite to the side on which the glass membrane was placed, so that the Nafion membrane reached the perforated plate surface.
  • Dupoint's DE2020: Nafion (registered trademark) solution several times from the side opposite to the side on which the glass membrane was placed, so that the Nafion membrane reached the perforated plate surface.
  • the obtained electrolyte membrane was sandwiched between an air electrode and a fuel electrode made in the same manner as in Example 1, pressed under the conditions of a temperature of 120 ° C and a pressure of lOkgf / cm 2 , and membrane electrode joining A body (MEA) was prepared. At this point, cracks occurred in the inorganic electrolyte glass on the electrolyte membrane surface. With the membrane electrode assembly fixed in place, the membrane / electrode assembly was subjected to a plurality of processes for taking in air and vaporized methanol. The fuel electrode conductive layer and the air electrode conductive layer were formed by sandwiching with gold foil having an opening. Furthermore, it was sandwiched between two resin frames while fixing the state as it was.
  • Sealing is performed by interposing a rubber O-ring between the air electrode side of the membrane electrode assembly and one frame, and between the fuel electrode side of the membrane electrode assembly and the other frame. did. Subsequently, the frame on the fuel electrode side was fixed to the liquid fuel tank with screws through a gas-liquid separation membrane. A 0.1 mm thick silicone sheet was used for the gas-liquid separation membrane. On the other hand, a porous plate was placed on the air electrode side frame to form a moisture retention layer. A stainless steel plate (SUS304) having the same configuration as that described in Example 1 was placed on the moisturizing layer to form a cover, and the entire cover was fixed by screws.
  • Example 1 As in Example 1, 5 ml of pure methanol was injected into the liquid fuel tank of the fuel cell prototyped as described above, and the voltage in an open circuit state at an environment of temperature 25 ° C and relative humidity 50%. The maximum output value was measured from the current value and voltage value. The maximum value of the surface temperature of the fuel cell was measured with a thermocouple attached to the cover surface. The measurement results are shown in Table 1 (Examination of measurement results of Examples and Comparative Examples) Table 1 shows the measurement results of the above examples:! To 3 and the comparative examples:!
  • This characteristic difference is considered to be caused by the degree of adhesion between the electrolyte membrane and the electrode affecting the impedance of the entire power generation system.
  • the electrolyte membrane surface is composed only of a highly rigid electrolyte, it is considered that the adhesion with the electrode is lowered and the output characteristics are lowered.
  • a high-power fuel cell is provided by disposing an electrolyte having a lower rigidity than the electrolyte inserted in the pore in the surface portion. It became clear that we could do it.
  • the present invention is not limited to the above-described embodiments as they are, but can be embodied by modifying the constituent elements without departing from the spirit of the invention in the implementation stage.
  • Various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiments. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, constituent elements over different embodiments may be appropriately combined.
  • a fuel storage is provided below the membrane electrode assembly (MEA).
  • MEA membrane electrode assembly
  • the fuel supply from the fuel storage part to the membrane electrode assembly may be connected through a flow path.
  • the configuration of the fuel cell body is a force-active type fuel cell that has been described by taking a passive type fuel cell as an example.
  • the present invention can also be applied to fuel cells.
  • the semi-passive type fuel cell the fuel supplied from the fuel container to the membrane electrode assembly is used for the power generation reaction, and then circulates back to the fuel container.
  • the semi-passive type fuel cell is different from the active type because it does not circulate the fuel, and does not impair the downsizing of the device.
  • Semi-passive fuel cells use a pump to supply fuel, and are different from pure passive methods such as internal vaporization.
  • a fuel shut-off valve may be arranged in place of the pump as long as fuel is supplied to the fuel accommodating part force membrane electrode assembly. In this case, the fuel cutoff valve is provided to control the supply of liquid fuel through the flow path.
  • a fuel cell with improved output characteristics is provided.

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  • 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

Pile à combustible comprenant une électrode à combustible, une électrode d'oxydation et une membrane électrolyte placée entre l'électrode à combustible et l'électrode d'oxydation. La membrane électrolyte comprend un matériau de base poreux (1), un premier électrolyte (4) appliqué dans les pores du matériau de base poreux (1) et un second électrolyte (2a, 2b) recouvrant les surfaces du matériau de base poreux (1). Le premier électrolyte (4) a un module de Young plus grand que celui du second électrolyte (2a, 2b).
PCT/JP2007/054199 2006-03-07 2007-03-05 Pile a combustible Ceased WO2007102469A1 (fr)

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JP2006-061426 2006-03-07

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Cited By (5)

* Cited by examiner, † Cited by third party
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WO2009078319A1 (fr) * 2007-12-14 2009-06-25 Toyota Jidosha Kabushiki Kaisha Membrane électrolytique pour pile à combustible et procédé de fabrication de la membrane électrolytique
JP2009146785A (ja) * 2007-12-14 2009-07-02 Kaneka Corp 固体高分子形燃料電池用電解質膜、該電解質膜を用いた膜−電極接合体、該電解質膜または該膜−電極接合体を用いた燃料電池、およびこれらの製造方法。
JP2010123388A (ja) * 2008-11-19 2010-06-03 Nissan Motor Co Ltd 電解質膜、ならびにそれを用いた膜電極接合体および燃料電池
JP2010199061A (ja) * 2009-01-28 2010-09-09 Dainippon Printing Co Ltd 燃料電池用電解質膜、燃料電池用膜・電極接合体及び燃料電池
US10333157B2 (en) 2014-11-25 2019-06-25 Johnson Matthey Fuel Cells Limited Membrane-seal assembly

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JP2005310606A (ja) * 2004-04-23 2005-11-04 Toyota Motor Corp 燃料電池用電解質層、燃料電池、および燃料電池用電解質層の製造方法
JP2006073235A (ja) * 2004-08-31 2006-03-16 Ube Ind Ltd 積層電解質膜およびその製造方法

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WO2000054351A1 (fr) * 1999-03-08 2000-09-14 Center For Advanced Science And Technology Incubation, Ltd. Membrane electrolytique pour pile a combustible et son procede de fabrication, et pile a combustible et son procede de fabrication
JP2001102071A (ja) * 1999-09-30 2001-04-13 Toshiba Corp 燃料電池および燃料電池の製造方法
JP2002075406A (ja) * 2000-08-30 2002-03-15 Sanyo Electric Co Ltd 燃料電池セルユニットとその製造方法
JP2002298867A (ja) * 2001-03-30 2002-10-11 Honda Motor Co Ltd 固体高分子型燃料電池
JP2004006306A (ja) * 2002-04-17 2004-01-08 Nec Corp 燃料電池、燃料電池用電極およびそれらの製造方法
JP2004193089A (ja) * 2002-10-17 2004-07-08 Toyobo Co Ltd 電解質膜−電極接合体
JP2004217921A (ja) * 2002-12-26 2004-08-05 Tokuyama Corp イオン交換膜及びその製造方法
JP2005268032A (ja) * 2004-03-18 2005-09-29 Toagosei Co Ltd 高分子電解質膜、その評価方法および燃料電池
JP2005310606A (ja) * 2004-04-23 2005-11-04 Toyota Motor Corp 燃料電池用電解質層、燃料電池、および燃料電池用電解質層の製造方法
JP2006073235A (ja) * 2004-08-31 2006-03-16 Ube Ind Ltd 積層電解質膜およびその製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009078319A1 (fr) * 2007-12-14 2009-06-25 Toyota Jidosha Kabushiki Kaisha Membrane électrolytique pour pile à combustible et procédé de fabrication de la membrane électrolytique
JP2009146758A (ja) * 2007-12-14 2009-07-02 Toyota Motor Corp 燃料電池用電解質膜及びその製造方法
JP2009146785A (ja) * 2007-12-14 2009-07-02 Kaneka Corp 固体高分子形燃料電池用電解質膜、該電解質膜を用いた膜−電極接合体、該電解質膜または該膜−電極接合体を用いた燃料電池、およびこれらの製造方法。
JP2010123388A (ja) * 2008-11-19 2010-06-03 Nissan Motor Co Ltd 電解質膜、ならびにそれを用いた膜電極接合体および燃料電池
JP2010199061A (ja) * 2009-01-28 2010-09-09 Dainippon Printing Co Ltd 燃料電池用電解質膜、燃料電池用膜・電極接合体及び燃料電池
US10333157B2 (en) 2014-11-25 2019-06-25 Johnson Matthey Fuel Cells Limited Membrane-seal assembly

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JPWO2007102469A1 (ja) 2009-07-23

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