WO2006100782A1 - 燃料電池 - Google Patents
燃料電池 Download PDFInfo
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- WO2006100782A1 WO2006100782A1 PCT/JP2005/005428 JP2005005428W WO2006100782A1 WO 2006100782 A1 WO2006100782 A1 WO 2006100782A1 JP 2005005428 W JP2005005428 W JP 2005005428W WO 2006100782 A1 WO2006100782 A1 WO 2006100782A1
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- WIPO (PCT)
- Prior art keywords
- fuel
- hollow fiber
- fuel cell
- fiber membrane
- gas
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/026—Wafer type modules or flat-surface type modules
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- 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
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- 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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0687—Reactant purification by the use of membranes or filters
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/06—External membrane module supporting or fixing means
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
-
- 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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0668—Removal of carbon monoxide or carbon dioxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—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]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a fuel cell, and more particularly to a fuel cell including a small, proton-conductive solid electrolyte layer.
- Mobile electronic devices such as mobile phones, portable information terminals, notebook computers, and digital cameras have a significant increase in power consumption tl as their functions increase. For this reason, there is a strong demand for higher output density and higher energy density of batteries used in portable electronic devices.
- a fuel cell is one in which electric energy is extracted from fuel by electrochemically reacting fuel and oxygen in the air.
- the theoretical energy density of the fuel itself in a fuel cell is several times higher than that of a lithium ion battery. If the power generation part of the fuel cell can be made smaller and react more efficiently than fuel, energy density far exceeding that of the secondary battery may be achieved. Under these circumstances, fuel cells are attracting attention as a power source that can replace lithium ion secondary batteries.
- Fuel cells are classified into alkaline, phosphoric acid, molten carbonate, solid oxide, and solid polymer types depending on the type of electrolyte used. Fuel cells installed in portable electronic devices are required to have a structure suitable for miniaturization and weight reduction, easy to start and stop, easy to handle, and strong to shock and vibration.
- a polymer electrolyte fuel cell is an all-solid type with a polymer membrane as an electrolyte.
- polymer electrolyte fuel cells are simple in structure, operate at low temperatures, and have quick start and stop operations, so they are fuel cells for portable electronic devices. Suitable as Direct methanol fuel cells (DMFC) that use methanol as fuel have been adopted especially for small portable electronic devices because of the high energy density of methanol, the ease of storage, and the simplicity of the battery structure.
- DMFC Direct methanol fuel cells
- DMFC a solid polymer electrolyte membrane having proton conductivity is sandwiched between two electrodes, and an aqueous methanol solution is supplied to the fuel electrode side.
- the electrochemical reaction that takes place at the fuel electrode is a reaction in which methanol reacts with water and is directly oxidized at the electrode, as shown below, to produce carbon dioxide, protons, and electrons.
- CH OH + HO ⁇ CO + 6H + + 6e- 0 Proton is a polymer
- Water is generated by passing through the solid electrolyte membrane and combining with oxygen in the catalyst layer of the air electrode. At this time, by connecting the fuel electrode and air electrode to an external circuit, electric power can be taken out by the generated electrons. The generated water is discharged out of the system as much as possible.
- a so-called vaporized supply type DMFC in which an aqueous methanol solution is vaporized and methanol is supplied to the catalyst layer of the fuel electrode in a gaseous state has been proposed.
- o Vaporization supply type DMFC has the advantage that methanol in liquid fuel can be used up even if the methanol concentration in the liquid fuel storage section decreases even if methanol concentration continues. .
- the vapor supply type DMFC can obtain a larger amount of power than the liquid supply type DMFC.
- FIG. 1A is a plan view of a conventional fuel cell
- FIG. 1B is a cross-sectional view of the fuel cell shown in FIG. 1A.
- the methanol aqueous solution is vaporized by the fuel retention layer 101, and the generated methanol gas is supplied to the fuel electrode 103 in contact with the solid electrolyte layer 102.
- the above reaction proceeds in the catalyst layer of the fuel electrode 103, and electrons generated by the reaction are taken out from the terminal 104 in contact with the fuel electrode 103.
- the terminal 104 is provided with a gas discharge port 105 and a liquid'gas separation membrane 106 for separating the liquid and the gas.
- the carbon dioxide gas generated at the fuel electrode 103 by liquid-gas separation is discharged to the outside.
- Patent Document 1 JP 2002-289224
- Patent Document 2 Japanese Patent Laid-Open No. 2001-102069
- Patent Document 1 discloses that the liquid 'gas separation membrane 106 permeates carbon dioxide gas.
- the liquid' gas separation membrane 106 discloses the methanol gas barrier property of the liquid 'gas separation membrane 106. ⁇ ⁇ If the liquid 'gas separation membrane 106 does not cut off the methanol gas, methanol gas leaks to the outside, which causes a problem that the amount of generated power with respect to the amount of methanol supplied decreases. Also, since methanol gas is flammable, excessive leakage to the outside may cause a fire such as ignition or explosion.
- a general object of the present invention is to provide a new and useful fuel cell that solves the above-described problems.
- a more specific object of the present invention is to provide a fuel cell capable of achieving both stable suppression of fuel gas leakage and high carbon dioxide emission capacity, high energy density, and stable power generation operation. It is.
- a power generation unit comprising a layer, a fuel storage unit that stores liquid fuel, a liquid fuel vaporization film that vaporizes the liquid fuel and supplies the vaporized fuel as a gaseous fuel to a fuel electrode, and the fuel electrode
- the product gas discharge unit has a hollow fiber membrane,
- the hollow fiber membrane is provided with a fuel cell characterized in that the generated surface gas is selectively discharged to the outside.
- a product gas discharge unit is provided between the fuel electrode and the liquid fuel vaporization film, and the product gas discharge unit selectively selects the generated gas generated at the fuel electrode as its surface force. It has a hollow fiber membrane that is taken in and discharged outside the fuel cell. Since the hollow fiber membrane has a larger surface area in direct contact with the mixed gas containing gaseous fuel and produced gas than the sheet-like gas separation membrane, the produced gas can be selectively and efficiently discharged outside the fuel cell. Therefore, it is possible to realize a fuel cell that achieves both suppression of leakage of fuel gas and high discharge capacity of product gas.
- the fuel cell of the present invention since the leakage of the fuel gas is suppressed, the ratio of the fuel gas contributing to power generation increases and the energy density increases. In addition, the increase in the pressure inside the fuel cell due to the generated gas can be suppressed, and the stoppage of power generation due to the increase in pressure can be avoided. Therefore, the fuel cell is highly stable and can generate power.
- FIG. 1A is a plan view of a conventional fuel cell.
- FIG. 1B is a cross-sectional view of the fuel cell shown in FIG. 1A.
- FIG. 2 is a cross-sectional view of a fuel cell according to an embodiment of the present invention.
- FIG. 3 is an exploded perspective view of the fuel cell shown in FIG. 2.
- FIG. 4 is a perspective view schematically showing a generated gas discharge part.
- FIG. 5 is an enlarged cross-sectional view showing a main part of a generated gas discharge part.
- FIG. 6 is a perspective view schematically showing another example of a generated gas discharge unit.
- FIG. 7A is a diagram showing a discharge characteristic of the example.
- FIG. 7B is a diagram showing a discharge characteristic of a comparative example.
- FIG. 2 is a cross-sectional view of the fuel cell according to the embodiment of the present invention.
- FIG. 3 is an exploded perspective view of the fuel cell shown in FIG.
- the fuel cell 10 includes a power generation unit 20, an air supply unit 30 that supplies oxygen gas to the air electrode 21, and a fuel gas such as methanol gas by vaporizing liquid fuel.
- the fuel supply unit is configured to supply 40 to the fuel electrode 23.
- the power generation unit 20 is configured by laminating an air electrode 21, a solid electrolyte layer 22, and a fuel electrode 23 in this order.
- the air electrode 21 is not shown because it is a thin film, it is composed of, for example, a porous carbon paper and a catalyst layer.
- the catalyst layer is, for example, a carbon powder force having Pt (platinum) fine particles or Pt supported on the surface thereof, and is disposed so as to be in contact with the solid electrolyte layer 22.
- the solid electrolyte layer 22 is made of a proton-conductive polymer solid electrolyte.
- the polymer solid electrolyte include a resin having a strong acid group such as a sulfone group and a phosphate group and a weak acid group such as a carboxyl group.
- naphthion (registered trademark) NF117 (DuPont product name) or Aciplex (Asahi Kasei product name) can be used. wear.
- the fuel electrode 23 is composed of a force not shown because it is a thin film, for example, a porous carbon paper and a catalyst layer.
- the catalyst layer is made of, for example, fine particles of a Pt (platinum) Ru (ruthenium) alloy or carbon powder carrying a Pt Ru alloy on the surface, and is disposed so as to be in contact with the solid electrolyte layer 22.
- fuel gas is supplied to the fuel electrode 23.
- liquid fuel that is the basis of the fuel gas
- methanol, dimethyl ether (DME), ethanol, or the like, or an aqueous solution thereof can be used.
- methanol aqueous solution a mixed solution of methanol and water or 100% concentration methanol (hereinafter abbreviated as “methanol aqueous solution”) will be described as an example.
- the reaction of the following reaction formula 1 proceeds, methanol gas and water vapor are consumed, diacid-carbon gas, proton (H +), electrons, dimethoxymethane as a by-product, Methyl formate and the like are produced. Dimethoxymethane and methyl formate undergo a different oxidation reaction from reaction formula 1 in the catalyst layer, generating protons and electrons.
- the protons conduct through the solid electrolyte layer 22 and reach the air electrode 21.
- the electrons perform work on a load connected as an external circuit (not shown) to the fuel cell via the anode gas diffusion layer 49 and the anode current collector 48. Further, the electrons reach the air electrode 21 through the air electrode current collector 33 and the air electrode gas diffusion layer 34.
- the reduction reaction of the following reaction formula 2 proceeds, and protons, electrons, and oxygen gas are consumed and water vapor is generated.
- the water vapor is discharged to the outside through the air electrode gas diffusion layers 32 and 34 and the oxygen supply port 3 la. Further, the carbon dioxide gas generated at the fuel electrode 23 is discharged to the outside by a product gas discharge unit 50 described later. In this way, the fuel cell 10 generates power using methanol as fuel.
- the air supply unit 30 diffuses oxygen introduced from the oxygen electrode side housing 31 and the oxygen supply port 31a of the air electrode side housing 31, and introduces oxygen into the air electrode 21. 32, 34, and cathode current collector 33.
- the air electrode side casing 31 is made of a metal material or a resin material cover.
- a resin material Although not limited, in terms of resistance to alcohols such as methanol, polyolefins such as polyethylene and polypropylene, fluorine resins such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyethylene (PFA), and polyvinyl chloride. It is preferable to use a resin such as polybutylene terephthalate, polyethylene naphthalate, polyethersulfone, polysulfone, polyphenylene oxide, polyetheretherketone, and acrylic.
- the air electrode side housing 31 is provided with a large number of oxygen supply ports 31a penetrating in the thickness direction.
- the oxygen supply port 3 la is preferably provided so that oxygen is uniformly introduced into the entire air electrode gas diffusion layer 32.
- the air electrode gas diffusion layer 32 is made of a porous material.
- the porous material is not particularly limited as long as it is porous, but suitable porous materials include, for example, ceramic porous material, carbon paper, carbon fiber nonwoven fabric, fluorine resin porous material, Polypropylene porous material etc. are mentioned.
- the air electrode current collector 33 has conductivity and has a mesh or porous structure.
- the air electrode current collector 33 allows air or oxygen gas to pass through the air electrode gas diffusion layer 32 to the air electrode gas diffusion layer 34 side.
- the air electrode current collector 33 is also preferably made of a metal material having high corrosion resistance such as Ni, SUS304, SUS316, and the like.
- a metal material having high corrosion resistance such as Ni, SUS304, SUS316, and the like.
- the structure of the air electrode current collector 33 include a metal mesh, an expanded metal, a metal nonwoven fabric, and a three-dimensional network structure foam metal.
- the air electrode current collector 33 is preferably formed on the surface thereof with a highly conductive and highly corrosion-resistant metal film, for example, an Au film. By providing such a metal film, it is possible to improve the corrosion resistance of the air electrode current collector 33 and reduce the contact resistance with the air electrode gas diffusion layer 34.
- the air electrode gas diffusion layer 34 is made of a conductive porous material.
- the conductive porous material include carbon paper and carbon fiber nonwoven fabric.
- oxygen gas in the air is introduced from the oxygen supply port 31a of the air electrode side casing 31, and the oxygen gas diffuses through the openings or pores of the air electrode gas diffusion layers 32 and 34. Then, it is uniformly introduced into the surface of the air electrode 21. Note that the air electrode gas diffusion layer 32 and the Z or air electrode gas diffusion layer 34 sufficiently oxygenate the surface of the air electrode 21 without providing them. If it can be supplied in a diffused state, there is no need to provide it!
- the sealing materials 56a to 56e are made of a resin having excellent airtightness, for example, a fluorine resin such as epoxy resin, olefin resin, PTFE, PFA, etc., and methanol or carbon dioxide inside the fuel cell 10. Gas or liquid such as aqueous methanol or water is prevented from leaking outside the fuel cell 10.
- a fluorine resin such as epoxy resin, olefin resin, PTFE, PFA, etc.
- methanol or carbon dioxide inside the fuel cell 10.
- Gas or liquid such as aqueous methanol or water is prevented from leaking outside the fuel cell 10.
- the fuel supply unit 40 includes a fuel electrode side casing 41, a fuel storage unit 42 filled with an aqueous methanol solution, a liquid fuel vaporization film 43 that vaporizes methanol in the aqueous methanol solution and converts it into methanol gas, Carbon dioxide provided between the anode gas diffusion layers 46 and 49 for diffusing methanol gas into the anode 23, the anode current collector 48, the liquid fuel vaporization membrane 43 and the anode gas diffusion layer 46 The product gas discharge part 50 etc. which discharge
- the fuel electrode side housing 41 is made of a metal material or a resin material.
- the resin material is not particularly limited, but in terms of resistance to alcohol such as methanol, polyolefins such as polyethylene and polypropylene, fluorine resin such as PTFE and PFA, polychlorinated butyl, polybutylene terephthalate, polyethylene naphthalate, poly It is preferable to use a resin such as ether sulfone, polysulfone, polyphenylene oxide, polyether ether ketone, and acrylic.
- the fuel storage part 42 is a void surrounded by the fuel electrode side casing 41 (or the porous material film 58), the liquid fuel vaporization film 43 facing the fuel electrode side casing 41, and the sealing material 56e.
- the fuel storage unit 42 stores the methanol aqueous solution filled from the fuel supply port 44.
- the aqueous methanol solution filled in the fuel storage unit 42 is in direct contact with the surface of the liquid fuel vaporization film 43. If the aqueous methanol solution in the liquid fuel vaporized film 43 has a good diffusion, the fuel storage unit 42 may be provided so as to contact a part of the liquid fuel vaporized film 43.
- a porous material film 58 having alcohol resistance may be provided between the fuel storage section 42 and the fuel supply port 44.
- a pressure application unit 45 that applies a back pressure to the methanol aqueous solution of the fuel storage unit 42 may be provided and connected to the fuel supply port 44.
- the pressure application unit 45 supplies a gas such as nitrogen gas to apply a back pressure to the fuel storage unit 42, that is, an aqueous methanol solution.
- a back pressure By applying such a back pressure, the vaporization rate of methanol in the liquid fuel vaporization film 43 described below is increased.
- the liquid fuel vaporized membrane 43 is non-porous, methanol Although the vaporization rate tends to decrease, by applying this pressure, the vaporization rate can be increased.
- the magnitude of the back pressure is appropriately selected depending on the material of the liquid fuel vaporization membrane 43 and the discharge capacity of carbon dioxide and carbon dioxide in the product gas discharge section 50, but may be set in the range of 0. OlMPa—IMPa. preferable.
- a fuel cartridge for storing an aqueous methanol solution is provided, the fuel cartridge is connected to the fuel supply port 44, and the aqueous methanol solution is continuously or temporarily removed from the fuel cartridge 42. May be supplied.
- a pressure application unit may be provided in the fuel cartridge, and the back pressure may be applied to the methanol solution in the fuel storage unit 42 by applying the back pressure to the methanol solution in the fuel cartridge via the gas described above. Also, install a separate pressure application unit and apply the back pressure directly to the methanol solution in the fuel storage unit 42.
- the liquid fuel vaporization film 43 is made of a porous material or non-porous material having a polymer isotropic force having an alcohol resistance such as methanol.
- Examples of the porous material suitable for the liquid fuel vaporized film 43 include a porous material made of fluororesin.
- the liquid fuel vaporization film 43 is preferably a non-porous material in that methanol is sufficiently vaporized.
- a non-porous material an aqueous methanol solution becomes a gas phase and passes through the material.
- a perfluorosulfonic acid-based resin is, for example, a resin having a main chain of fluorine resin and a side chain having a sulfonic acid group.
- Examples of the resin film of such a material include naphthion (registered trademark) manufactured by DuPont and aciplex manufactured by Asahi Kasei.
- a resin mainly composed of a perfluorocarbon-based resin having a carboxyl group may be mentioned.
- the perfluorocarbon-based resin having a carboxyl group is, for example, a resin having a main chain of fluorine resin and a side chain having a carboxyl group.
- Asahi Glass Examples include the product name Flemion manufactured by a subsidiary.
- non-porous material suitable for the liquid fuel vaporized film 43 a resin mainly composed of one of polysulfone, polyimide, polyetheretherketone and polyamide can be mentioned. Furthermore, examples of the non-porous material suitable for the liquid fuel vaporized film 43 include a polymer material containing silicone such as silicone rubber.
- the fuel gas diffusion layer 46 is made of a porous material having alcohol resistance such as methanol.
- the porous material suitable for the fuel gas diffusion layer 46 include porous materials such as ceramics, carbon paper, carbon fiber nonwoven fabric, fluorine resin, and polypropylene.
- the porosity of the fuel gas diffusion layer 46 is preferably set in the range of 30% -95%, more preferably in the range of 40% -90%. When the porosity exceeds 95%, the mechanical strength of the fuel gas diffusion layer 46 decreases.
- the thickness of the fuel gas diffusion layer 46 is not particularly limited! /, But is preferably 1 mm or less. If the fuel gas diffusion layer 46 is thicker than lmm, the thickness of the entire fuel cell becomes excessively large. As described above, it is preferable to provide the fuel gas diffusion layer 46, but it is not essential when the fuel gas is sufficiently diffused.
- the fuel electrode current collector 48 is made of the same material as the air electrode current collector 33, and a highly conductive and highly corrosion-resistant metal film such as an Au film can be formed on the surface thereof. preferable.
- the fuel gas diffusion layer 49 is made of a conductive porous material having resistance to alcohol such as methanol.
- the conductive porous material include carbon paper and carbon fiber nonwoven fabric.
- a generated gas discharge unit 50 is provided between the liquid fuel vaporization film 43 and the fuel gas diffusion layer 46.
- the generated gas discharge unit 50 will be described with reference to FIGS. 2 and 3 and FIGS. 4 and 5.
- FIG. 4 is a perspective view schematically showing the product gas discharge unit.
- FIG. 5 is an enlarged cross-sectional view showing the main part of the product gas discharge part.
- the product gas discharge section 50 has a bundle 51 of a plurality of hollow fiber membranes 52 having gas selectivity (hereinafter, a "bundle of a plurality of hollow fiber membranes 52" is referred to as a “hollow fiber membrane bundle 51"). And both ends 52-1 of the hollow fiber membrane 52 are composed of a fixing material 53 that fixes the two to each other.
- the hollow fiber membrane bundle 51 is a liquid fuel vaporization membrane 4 3 and the fuel gas diffusion layer 46 are exposed to a gas mixture containing high concentrations of methanol gas, carbon dioxide, water vapor, and by-products of the reaction at the fuel electrode 23.
- each hollow fiber membrane 52 is exposed to the outside of the fuel cell 10 through the fixing material 53.
- Each of the two adhering members 53 is a side surface of the fuel cell 10, that is, as shown in FIG. 2, the fuel cell 10 perpendicular to the Y-axis direction when the stacking direction of each member constituting the fuel cell is the X-axis direction. It is provided on the outer surface.
- the fixing material 53 fixes the hollow fiber membranes 52 to each other and seals the mixed gas between the adjacent hollow fiber membranes 52 and the hollow fiber membranes 52 so that the mixed gas does not leak outside. Further, the hollow fiber membranes 52 are fixed to each other so that the hollow portion 52 a is not crushed by the fixing material 53.
- the hollow fiber membrane 52 has a hollow portion 52 a that opens to the outside of the fuel cell 10.
- the fixing material 53 is made of, for example, thermoplastic resin (for example, polyolefin) or thermosetting resin (for example, epoxy resin).
- the hollow fiber membrane 52 is a thread having a separation layer with high gas selective permeability and having a hollow core.
- the hollow fiber membrane 52 has a hollow portion 52a at its core, a high-pressure gas separation layer 52b on its outer surface, and a multi-hole with good gas permeability on its inner side. Consists of a stratum 52c. That is, the hollow fiber membrane 52 also has different material forces on the outside and inside! It is a so-called asymmetric membrane.
- the separation layer 52b also has a non-porous glassy polymer force.
- Suitable glassy polymers for separation layer 52b include polysulfone, polyimide, polyamide, and mixtures thereof. These glassy polymers have particularly good resistance to alcohol and good thermal properties with high mechanical strength.
- the soft spot of the glassy polymer is preferably in the range of 150 ° C. to 420 ° C. from the viewpoint of good alcohol resistance and good gas selective permeability.
- the separation layer 52b Since the separation layer 52b is non-porous, it has gas selective permeability according to the size of gas molecules.
- the size of the gas molecules contained in the mixed gas is related to water vapor, carbon dioxide, methanol, methyl formate, and ditoxymethane.
- the separation layer 52b transmits more gas having a small molecular size. That is, carbon dioxide has a smaller molecule than methanol, so it hardly permeates methanol and selectively permeates carbon dioxide. Since water vapor has a smaller molecular size than carbon dioxide and carbon dioxide, separation layer 52b transmits water vapor. To do.
- the separation layer 52b is preferable from the viewpoint of preventing condensation of water in the fuel electrode gas diffusion layers 46 and 49, since it transmits more water vapor when the partial pressure of water vapor is high, that is, when the water vapor is excessive.
- the porous layer 52c is made of a porous polymer. Since the porous layer 52c is porous, the gas permeation rate is high. In the porous layer 52c, a higher porosity is preferable in terms of a higher gas permeation rate, but if the porosity is excessively high, the support function of the hollow fiber membrane is lowered.
- the porous layer 52c may be made of the same material as the separation layer 52b or a different material force.
- the thickness of the separation layer 52b of the hollow fiber membrane 52 is preferably lOnm—200 nm (more preferably 20 nm—1 OO nm). If the thickness of the separation layer 52b is less than lOnm, it becomes difficult to manufacture and the gas selective permeability is lowered, and if it exceeds 200 nm, the gas permeation rate is lowered.
- the thickness of the porous layer 52c of the hollow fiber membrane 52 is preferably 20 ⁇ m-200 m (more preferably 30 ⁇ m-100 ⁇ m).
- the thickness of the porous layer 52c is less than 20 ⁇ m, the mechanical strength of the hollow fiber membrane decreases, and when it exceeds 200 m, the permeation resistance of the porous layer 52c increases and the permeation speed decreases.
- the outer diameter of the hollow fiber membrane 52 is preferably 1000 ⁇ m or less. When the outer diameter exceeds 1000 ⁇ m, the effect of increasing the surface area is reduced.
- the inner diameter of the hollow fiber membrane 52 (that is, the diameter of the hollow portion) is 30 m to 500 m.
- the inner diameter exceeds 500 m
- the outer diameter also increases, so the effect of increasing the hollow fiber membrane 52 (increasing surface area) decreases. Also, if the inner diameter is less than 30 m, it becomes difficult to manufacture.
- the hollow fiber membrane bundle 51 is not limited to the force 8 in which eight hollow fiber membranes 52 are shown in FIG. 4, and the number of hollow fiber membranes 52 is the amount of carbon dioxide generated at the fuel electrode. It is appropriately selected according to. Further, in FIG. 4, the hollow fiber membranes 52 may have two or more forces arranged in one row in the longitudinal direction.
- the number density of the hollow fiber membranes 52 of the hollow fiber membrane bundle 51 that is, the number of the hollow fiber membranes 52 per unit area in the cross section perpendicular to the longitudinal direction of the hollow fiber membrane bundle 51 is 100 / cm 2 — 25 00 Preferable to be Zcm 2 ! /.
- the hollow fiber membranes 52 are preferably converged substantially in parallel. In this way, more hollow fiber membranes 52 can be arranged per unit volume occupied by the hollow fiber membrane bundle 51, and both high carbon dioxide emission capacity and downsizing of the generated gas discharge unit 50 are achieved. it can.
- the hollow fiber membrane bundle 51 preferably has a gap between the adjacent hollow fiber membranes 52 and 52. This facilitates the diffusion of methanol gas and carbon dioxide.
- the hollow fiber membranes 52 may be converged in a so-called twilled state in which the hollow fiber membrane bundles 51 are alternately crossed at a low angle with respect to the axial direction of the hollow fiber membrane bundle 51. Further, the hollow fiber membrane 52 may be converged substantially in parallel with the central portion of the hollow fiber membrane 52 only in the twill weave state. Further, the hollow fiber membrane 52 may be converged into a plain weave state composed of warp and weft. Although not shown in the case of the plain weave state, the fixing member 53 for fixing the end of the hollow fiber membrane 52 corresponding to the warp may be arranged on the upper and lower surfaces of the fuel cell 10 shown in FIG.
- the UBE N separator (nitrogen separation membrane device manufactured by Ube Industries) is used as the hollow fiber membrane 52.
- a hollow fiber membrane made of polyimide or a hollow fiber membrane of SEPAREL (registered trademark, manufactured by Dainippon Ink & Chemicals, Inc., a diacid-carbon separation membrane device) can be used.
- the hollow fiber membrane 52 can be manufactured by, for example, a method disclosed in JP 2002-172311 A. The method is to form a polymer mixture solution obtained by dissolving a mixture of two or more polymers containing at least one of the above polymers in a solvent by a so-called dry and wet method. Specifically, the polymer mixture solution is extruded from a nozzle cover to form a hollow fiber-like formed product, which is passed through air or nitrogen atmosphere and then immersed in a coagulation bath. Phase separation. Thereafter, the solvent is removed by drying to form a hollow fiber membrane.
- the hollow fiber membrane bundle 51 is disposed between the liquid fuel vaporization membrane 43 and the fuel gas diffusion layer 46, and is water, methanol, and product gas. It is exposed to a gas mixture containing di-carbon dioxide. Among the mixed gas, carbon dioxide selectively permeates through the separation layer 52b of the hollow fiber membrane 52 to reach the hollow portion 52a, and is discharged from the end portions 52-1 on both sides of the hollow fiber membrane to the outside of the fuel cell 10. Is done.
- the product gas discharge unit 50 is provided with the hollow fiber membrane bundle 51 including the hollow fiber membranes 52 between the liquid fuel vaporization membrane 43 and the fuel gas diffusion layer 46. Therefore hollow The thread membrane 52 can take a larger surface area in direct contact with a mixed gas containing methanol, carbon dioxide, carbon dioxide, etc. than the sheet-like gas separation membrane. Can be discharged outside. That is, the hollow fiber membrane 52 has a high discharge capacity for carbon dioxide.
- the conventional product gas discharge section is provided with a gas separation membrane in a partial region of the fuel electrode.
- the produced gas discharge unit 50 can arrange the hollow fiber membrane bundle 51 having an area substantially the same as that of the fuel electrode 23 between the liquid fuel vaporization membrane 43 and the fuel gas diffusion layer 46. Therefore, since the product gas discharge part 50 can take a large surface area in direct contact with the mixed gas in this respect, the discharge capacity of carbon dioxide is high.
- the generated gas discharge unit 50 discharges the carbon dioxide from the surface of the hollow fiber membrane 52 to the outside from the end 52-1 of the hollow fiber membrane 52, the surface area of the hollow fiber membrane 52 is increased. On the other hand, the area of the fixing material 53 can be greatly reduced. Accordingly, since the fixing material 53 can be reduced in size, the fuel cell 10 can be reduced in size, particularly a thin plate.
- the hollow fiber membrane 52 is excellent in gas selective permeability, it is possible to greatly suppress the leakage of methanol to the outside of the fuel cell 10. Therefore, the fuel cell 10 has high safety and can increase the energy density because methanol that contributes to power generation increases.
- the fuel cell 10 has high power generation stability.
- the product gas discharge section 50 is not limited to be provided between the liquid fuel vaporization film 43 and the fuel gas diffusion layer 46, and may be provided between the liquid fuel vaporization film 43 and the fuel electrode 23. However, it is necessary that the hollow portion 52a is not blocked by the crushing or breaking of the hollow fiber membrane 52.
- the hollow fiber membrane 52 has the separation layer 52b and the porous layer 52c clearly separated as shown in FIG. 5, but the separation layer 52b and the porous layer 52c are preferably separated from each other. There is no clear boundary.
- the hollow fiber membrane 52 preferably has the separation layer 52b arranged on the outside in terms of alcohol resistance. However, the separation layer 52b may be on the inside and the porous layer 52c may be on the outside. The separation layer 52b may be sandwiched between the porous layers 52c. In this case, the porous layer disposed on the outer side is preferably made of a material having excellent alcohol resistance.
- the hollow fiber membrane 52 is not limited to the asymmetric membrane described above, and may be a gas separation membrane having gas selective permeability of carbon dioxide and methanol. As such a hollow fiber membrane 52, for example, melt spinning that also becomes polyolefine can be mentioned.
- the hollow fiber membrane bundle 51 of the product gas discharge unit 50 has been described with the longitudinal direction parallel to the X-axis direction, but the longitudinal direction of the hollow fiber membrane bundle 51 is Z-axis. It may be parallel to the direction. That is, the fixing material 53 shown in FIG. 4 is provided on the side surface perpendicular to the Z-axis direction of the fuel cell shown in FIG. Note that the product gas discharge unit shown in FIG. 6 may be provided instead of the product gas discharge unit shown in FIG.
- FIG. 6 is a perspective view schematically showing another example of the product gas discharge unit.
- the same reference numerals are assigned to portions corresponding to the portions described above, and the description thereof is omitted.
- the product gas discharge section 60 includes a hollow fiber bundle 61 having a number of hollow fiber membranes 52 curved in a U shape, and both ends 52 — of the hollow fiber membrane 52. Consists of one adhesive 63 for fixing 1. Further, a sealing material 64 having the same size as the fixing material 63 is provided on the side surface of the fuel cell opposite to the fixing material 63.
- the hollow fiber membrane 51 extends along the surface of the liquid fuel vaporization membrane 43 in the direction from the fixing material 63 to the sealing material 64, is bent near the sealing material 64, and returns to the fixing material 63 again. Extend. Thus, both end portions 52-1 of the hollow fiber membrane 52 are exposed on one side surface of the fuel cell (the outer surface perpendicular to the Y-axis direction or the Z-axis direction shown in FIG. 2). By doing so, the structure of the product gas discharge section 60 can be simplified, and the structure of the fuel cell 10 can be simplified.
- the fixing material 63 has the same material force as that of the fixing material 53 shown in FIG. Further, the sealing material 64 has the same material force as the sealing material 56 shown in FIG.
- a fuel cell having the same configuration as that of the fuel cell shown in FIGS. 2 and 3 was formed.
- the specific configuration of the product gas discharge unit was the same as that of the product gas discharge unit shown in Fig. 4. The following description will be given with reference to FIGS.
- the size of the power generation unit 20 was 40 mm long and 40 mm wide.
- the following materials were used for the fuel cells according to the examples.
- a Pt—Ru alloy supported catalyst TEC61E54 was used for the catalyst layer of the fuel electrode 23, and a platinum supported catalyst TEC10E50E (manufactured by Tanaka Kikinzoku Co., Ltd.) was used for the catalyst layer of the air electrode 21.
- Solid electrolyte naphthion (registered trademark) NF117 (trade name, manufactured by DuPont) was used for the solid electrolyte layer 22.
- the carbon electrode (thickness 280 m, made of Torayen earth) was used for the air electrode gas diffusion layers 32 and 34, and mesh SUS 304 was used for the air electrode current collector.
- the hollow fiber membrane bundle 51 has a UBE N separator hollow fiber membrane (outer diameter 400 m) 70
- a book was bundled and provided between the liquid fuel vaporization film 43 and the anode electrode gas diffusion layer 46.
- An epoxy resin was used for the fixing material 53, and the area of the fixing material was set to 0.03 cm 2 . Note that epoxy resin having excellent airtightness was used for the sealing materials 56a to 56e.
- the generated gas discharge part is provided with two carbon papers (thickness 280 ⁇ m, manufactured by Toray Industries, Inc.) instead of the hollow fiber membrane bundle so as to cover the fuel electrode gas diffusion layer.
- the configuration was the same as in the example except for the above.
- the fuel amount was the same as in the example.
- discharge time the time from the start to the end of discharge.
- voltage during discharge was measured, and the time average was obtained to obtain the average discharge voltage. It was confirmed that no methanol remained in the fuel storage portions of the fuel cells of Examples and Comparative Examples at the end of each cycle discharge.
- FIG. 7A is a diagram showing the continuous discharge characteristics of the fuel cell according to the example.
- FIG. 7B is a diagram showing the continuous discharge characteristics of the fuel cell according to the comparative example.
- the discharge time of each cycle of the first cycle force and the third cycle is 21% longer than the comparative example. This is because, in the fuel cell of the comparative example, methanol leaked from the carbon plate to the outside, whereas in the fuel cell of the example, the generated gas discharge part having the hollow fiber membrane bundle was generated at the fuel electrode. In addition to discharging carbon dioxide and suppressing leakage of methanol to the outside, the amount of methanol that contributed to electricity generation increased and the discharge time was prolonged. In addition, it was found that the fuel cell of the example operates stably even when methanol is replenished repeatedly and can maintain discharge characteristics.
- the fuel cell of the example had a higher ability to discharge carbon dioxide and the fuel utilization efficiency higher than the fuel cell of the comparative example.
- the suppression of fuel gas leakage and the high emission capacity of carbon dioxide and carbon dioxide are compatible, and the energy density is high and the generation of energy is high.
- a fuel cell capable of electric operation can be provided.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007509135A JP4751383B2 (ja) | 2005-03-24 | 2005-03-24 | 燃料電池 |
KR1020077021889A KR100933246B1 (ko) | 2005-03-24 | 2005-03-24 | 연료 전지 |
CN2005800492607A CN101151760B (zh) | 2005-03-24 | 2005-03-24 | 燃料电池 |
PCT/JP2005/005428 WO2006100782A1 (ja) | 2005-03-24 | 2005-03-24 | 燃料電池 |
EP05726981A EP1863113B1 (en) | 2005-03-24 | 2005-03-24 | Fuel cell |
US11/854,184 US7544436B2 (en) | 2005-03-24 | 2007-09-12 | Fuel cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2005/005428 WO2006100782A1 (ja) | 2005-03-24 | 2005-03-24 | 燃料電池 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/854,184 Continuation US7544436B2 (en) | 2005-03-24 | 2007-09-12 | Fuel cell |
Publications (1)
Publication Number | Publication Date |
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WO2006100782A1 true WO2006100782A1 (ja) | 2006-09-28 |
Family
ID=37023479
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2005/005428 WO2006100782A1 (ja) | 2005-03-24 | 2005-03-24 | 燃料電池 |
Country Status (6)
Country | Link |
---|---|
US (1) | US7544436B2 (ja) |
EP (1) | EP1863113B1 (ja) |
JP (1) | JP4751383B2 (ja) |
KR (1) | KR100933246B1 (ja) |
CN (1) | CN101151760B (ja) |
WO (1) | WO2006100782A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007227154A (ja) * | 2006-02-23 | 2007-09-06 | Casio Comput Co Ltd | 燃料電池装置 |
JP2008171817A (ja) * | 2007-01-09 | 2008-07-24 | Samsung Sdi Co Ltd | 直接メタノール燃料電池用co2セパレータ |
KR100970401B1 (ko) | 2007-01-09 | 2010-07-15 | 삼성에스디아이 주식회사 | 직접 메탄올 연료 전지용 co2 세퍼레이터 |
CN109921074A (zh) * | 2019-01-21 | 2019-06-21 | 西安交通大学 | 低功耗物料分离传输直接甲醇燃料电池及其工作方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100040926A1 (en) * | 2008-06-23 | 2010-02-18 | Nuvera Fuel Cells, Inc. | Consolidated fuel cell electrode |
US8268498B2 (en) * | 2009-03-27 | 2012-09-18 | Sony Corporation | Fuel cell, fuel cell system, and electronic device |
CN109888341B (zh) * | 2019-01-21 | 2020-12-15 | 西安交通大学 | 一种物料分离传输直接甲醇燃料电池及其工作方法 |
CN109830723B (zh) * | 2019-01-21 | 2020-10-27 | 西安交通大学 | 蓄能驱动物料分离传输直接甲醇燃料电池及其工作方法 |
CN114086198B (zh) * | 2021-12-15 | 2022-11-08 | 中国科学院大连化学物理研究所 | 一种固体氧化物电解池膜电极的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001199315A (ja) * | 1999-11-11 | 2001-07-24 | Ube Ind Ltd | 中空糸分離膜を用いて乾燥窒素をタイヤへ充填する方法 |
JP2002373677A (ja) * | 2001-06-15 | 2002-12-26 | Toshiba Corp | 燃料電池 |
JP2003100315A (ja) * | 2001-09-25 | 2003-04-04 | Hitachi Ltd | 燃料電池発電装置とそれを用いた装置 |
JP2005032520A (ja) * | 2003-07-10 | 2005-02-03 | Fujitsu Ltd | 燃料電池及びその製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6048383A (en) * | 1998-10-08 | 2000-04-11 | International Fuel Cells, L.L.C. | Mass transfer composite membrane for a fuel cell power plant |
JP2001102069A (ja) | 1999-09-29 | 2001-04-13 | Toshiba Corp | 燃料電池 |
JP3496934B2 (ja) | 2001-03-23 | 2004-02-16 | 株式会社東芝 | 燃料電池 |
US6811905B1 (en) * | 2002-05-21 | 2004-11-02 | Giner Electro Chemical Systems, Llc | Direct organic fuel cell having a vapor transport member |
CN1532973A (zh) * | 2003-03-21 | 2004-09-29 | 乐金电子(天津)电器有限公司 | 燃料电池的热利用系统以及其控制方法 |
US7407721B2 (en) * | 2003-04-15 | 2008-08-05 | Mti Microfuel Cells, Inc. | Direct oxidation fuel cell operating with direct feed of concentrated fuel under passive water management |
-
2005
- 2005-03-24 CN CN2005800492607A patent/CN101151760B/zh not_active Expired - Fee Related
- 2005-03-24 JP JP2007509135A patent/JP4751383B2/ja not_active Expired - Fee Related
- 2005-03-24 WO PCT/JP2005/005428 patent/WO2006100782A1/ja not_active Application Discontinuation
- 2005-03-24 EP EP05726981A patent/EP1863113B1/en not_active Expired - Fee Related
- 2005-03-24 KR KR1020077021889A patent/KR100933246B1/ko not_active IP Right Cessation
-
2007
- 2007-09-12 US US11/854,184 patent/US7544436B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001199315A (ja) * | 1999-11-11 | 2001-07-24 | Ube Ind Ltd | 中空糸分離膜を用いて乾燥窒素をタイヤへ充填する方法 |
JP2002373677A (ja) * | 2001-06-15 | 2002-12-26 | Toshiba Corp | 燃料電池 |
JP2003100315A (ja) * | 2001-09-25 | 2003-04-04 | Hitachi Ltd | 燃料電池発電装置とそれを用いた装置 |
JP2005032520A (ja) * | 2003-07-10 | 2005-02-03 | Fujitsu Ltd | 燃料電池及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1863113A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007227154A (ja) * | 2006-02-23 | 2007-09-06 | Casio Comput Co Ltd | 燃料電池装置 |
JP2008171817A (ja) * | 2007-01-09 | 2008-07-24 | Samsung Sdi Co Ltd | 直接メタノール燃料電池用co2セパレータ |
KR100970401B1 (ko) | 2007-01-09 | 2010-07-15 | 삼성에스디아이 주식회사 | 직접 메탄올 연료 전지용 co2 세퍼레이터 |
US8871396B2 (en) | 2007-01-09 | 2014-10-28 | Samsung Sdi Co., Ltd. | CO2 separator for direct methanol fuel cell system |
CN109921074A (zh) * | 2019-01-21 | 2019-06-21 | 西安交通大学 | 低功耗物料分离传输直接甲醇燃料电池及其工作方法 |
Also Published As
Publication number | Publication date |
---|---|
KR100933246B1 (ko) | 2009-12-22 |
CN101151760A (zh) | 2008-03-26 |
KR20070108257A (ko) | 2007-11-08 |
JPWO2006100782A1 (ja) | 2008-08-28 |
EP1863113B1 (en) | 2012-12-05 |
CN101151760B (zh) | 2010-09-15 |
US7544436B2 (en) | 2009-06-09 |
US20080003475A1 (en) | 2008-01-03 |
EP1863113A1 (en) | 2007-12-05 |
JP4751383B2 (ja) | 2011-08-17 |
EP1863113A4 (en) | 2011-06-29 |
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