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WO2006083038A1 - Pile a combustible - Google Patents

Pile a combustible Download PDF

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Publication number
WO2006083038A1
WO2006083038A1 PCT/JP2006/302311 JP2006302311W WO2006083038A1 WO 2006083038 A1 WO2006083038 A1 WO 2006083038A1 JP 2006302311 W JP2006302311 W JP 2006302311W WO 2006083038 A1 WO2006083038 A1 WO 2006083038A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte membrane
catalyst layer
catalyst
gas diffusion
fuel cell
Prior art date
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Ceased
Application number
PCT/JP2006/302311
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English (en)
Japanese (ja)
Inventor
Haruyuki Nakanishi
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Toyota Motor Corp
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Toyota Motor Corp
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Filing date
Publication date
Application filed by Toyota Motor Corp filed Critical Toyota Motor Corp
Publication of WO2006083038A1 publication Critical patent/WO2006083038A1/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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/861—Porous electrodes with a gradient in the porosity
    • 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
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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 including a cell module having a hollow electrolyte membrane.
  • a fuel cell directly converts chemical energy into electrical energy by supplying fuel and an oxidant to two electrically connected electrodes and causing the fuel to oxidize electrochemically. Unlike thermal power generation, it is not subject to the Carnot cycle, so it exhibits high energy conversion efficiency.
  • the solid polymer electrolyte fuel cell is a fuel cell that uses a solid polymer electrolyte membrane as an electrolyte, and has advantages such as easy miniaturization and operation at a low temperature. It is attracting attention as a power source for mobiles.
  • Eq. (1) The electrons generated in Eq. (1) reach the force sword after working with an external load via an external circuit. And the proton produced by the formula (1) is hydrated with water. In the solid polymer electrolyte membrane, it moves from the anode side to the force sword side by electroosmosis.
  • the fuel cell is a clean power generation device having no emission other than water.
  • a solid polymer electrolyte fuel cell a planar membrane / electrode joint obtained by mainly providing a catalyst layer serving as an anode and a force sword on the other surface of a planar solid polymer electrolyte membrane is obtained.
  • a fuel cell stack has been developed that is obtained by stacking a plurality of flat single cells produced by further providing gas diffusion layers on both sides of the body and finally sandwiching them with a planar separator. I came.
  • a proton conductive polymer membrane having a very thin film thickness is used as the solid polymer electrolyte membrane.
  • This film thickness is typically less than 100 um; even if a thinner electrolyte membrane is used to further increase the power density, the thickness of a single cell can be drastically reduced from the current one. I can not do such a thing.
  • the catalyst layer, gas diffusion layer, separator, etc. are also being made thinner, but there is a limit to improving the output density per unit volume even by making all these members thinner. is there.
  • a sheet-like carbon material having excellent corrosivity is usually used for the separator.
  • This carbon material itself is also expensive, but it also has a flat membrane / electrode contact.
  • a groove serving as a gas flow path is usually finely processed on the surface of the separator. It became expensive and pushed up the manufacturing cost of fuel cells.
  • the flat single cell must be surely sealed at the periphery of a plurality of single cells stacked so that fuel gas and oxidant gas do not leak from the gas flow path.
  • problems such as technical difficulties, and power generation efficiency may decrease due to deflection or deformation of the planar membrane-electrode assembly.
  • solid polymer electrolyte fuel cells have been developed that use a cell module with electrodes on the inner and outer surfaces of a hollow electrolyte membrane as a basic power generation unit.
  • a member corresponding to a separator used in a flat type Since different types of gas are supplied to the inner surface and the outer surface for power generation, it is not necessary to form a gas flow path. Therefore, the manufacturing cost is expected to be reduced. Furthermore, since the cell module has a three-dimensional shape, the specific surface area relative to the volume can be increased compared to a flat single cell, and the power generation output density per volume can be expected to improve.
  • the electrodes provided on the inner surface side and outer surface side of the hollow electrolyte membrane are usually the catalyst layer in order from the electrolyte membrane side.
  • a gas diffusion layer a gas diffusion layer.
  • the reaction gas (oxidant gas, fuel gas) supplied to the gas diffusion layer diffuses in the gas diffusion layer, reaches the catalyst surface in the catalyst layer, and causes the above-described electrochemical reaction.
  • reaction gas since a sufficient amount of reaction gas necessary for power generation is supplied to the catalyst layer, it is desirable that the gas diffusion from the gas diffusion layer to the catalyst layer is high, but on the other hand, the catalyst on the electrolyte membrane side When the gas flow is intense in the layer, the reaction gas tends to remove moisture from the catalyst layer and the electrolyte membrane, and the ratio of reaction components that cause a reaction on the catalyst surface may be reduced.
  • the present invention has been accomplished in view of the above circumstances, and a sufficient amount of reaction gas is supplied, the utilization efficiency of reaction components in the supplied reaction gas is improved, and the electrolyte membrane is dried.
  • An object of the present invention is to provide a fuel cell that can be suppressed. Disclosure of the invention
  • the fuel cell of the present invention is a fuel cell comprising a cell module having a hollow electrolyte membrane and a pair of electrodes provided on the hollow inner surface and outer surface of the electrolyte membrane, wherein at least one of the pair of electrodes is A catalyst layer and a gas diffusion layer in order from the electrolyte membrane side, and the porosity of the catalyst layer decreases from the gas diffusion layer side toward the electrolyte membrane side. It is characterized by having a distribution.
  • the diffusibility of the reaction gas in the thickness direction of the catalyst layer can be adjusted. That is, on the gas diffusion layer side, the porosity of the catalyst layer is large, a sufficient amount of reaction gas for power generation can be taken from the gas diffusion layer, and the taken reaction gas is sufficiently diffused into the catalyst layer. Can do. On the other hand, on the electrolyte membrane side, the porosity of the catalyst layer is small, and more reaction components come into contact with the catalyst, so the amount of reaction components contributing to the electrochemical reaction increases. As a result, the utilization efficiency of the reaction gas can be improved, and furthermore, cross-reaction in which the reaction components in the reaction gas permeate the electrolyte membrane in a molecular state can be prevented.
  • the catalyst layer preferably further has a distribution in which the amount of catalyst component per unit volume increases from the gas diffusion layer side toward the electrolyte membrane side.
  • Cross leak is a force that easily occurs on the anode side when hydrogen is used as a fuel.
  • the anode has a catalyst layer and a gas diffusion layer in order from the electrolyte membrane side.
  • the catalyst layer of the anode further has a unit volume. It is preferable that the catalyst component amount has a distribution that increases from the gas diffusion layer side toward the electrolyte membrane side.
  • the porosity of the catalyst layer is 80 to 90% from the gas diffusion layer side to the one-third thickness of the catalyst layer, and from the gas diffusion layer side.
  • the catalyst layer thickness is 70 to 80% from 1/3 to 2/3, and 60 to 70% from the gas diffusion layer side to the catalyst layer thickness from 2/3 to the electrolyte membrane side.
  • the fuel cell of the present invention can supply a sufficient amount of reaction gas necessary for power generation to the catalyst layer, and can increase the amount of reaction components contributing to the electrochemical reaction in the reaction gas. It is possible to improve the power generation performance and reaction gas utilization efficiency of the fuel cell. In addition, by improving the utilization efficiency of the reaction gas, it is possible to prevent a cross leak in which hydrogen and oxygen permeate through the electrolyte membrane in a molecular state, thereby extending the life of the fuel cell. Furthermore, by preventing the electrolyte membrane and the catalyst layer from drying, the power generation performance of the fuel cell can be improved.
  • FIG. 1 is a schematic view showing one embodiment of a cell module provided in the fuel cell of the present invention.
  • FIG. 2 is a partially enlarged sectional view of the cell module.
  • 1 0 1 is a cell module
  • 1 is a hollow electrolyte membrane (perfluorocarbon sulfonic acid resin membrane)
  • 2 is a force sword
  • 3 is an anode
  • 4 is a cathode catalyst layer
  • 5 is a force sword gas diffusion layer
  • 6 is an anode catalyst layer
  • 7 is a cathode gas diffusion layer
  • 8 is a hollow portion
  • 9 and 10 are current collectors.
  • the fuel cell of the present invention is a fuel cell comprising a cell module having a hollow electrolyte membrane and a pair of electrodes provided on the hollow inner surface and outer surface of the electrolyte membrane, wherein at least one of the pair of electrodes is A catalyst layer and a gas diffusion layer are provided in order from the electrolyte membrane side, and the porosity of the catalyst layer has a distribution that decreases from the gas diffusion layer side toward the electrolyte membrane side.
  • the fuel cell of the present invention will be described by taking as an example the case where a solid polymer electrolyte membrane which is a kind of proton conductive membrane is used as the electrolyte membrane.
  • a perfluorocarbon sulfonic acid resin membrane is used as the solid polymer electrolyte membrane.
  • FIG. 1 is a diagram showing an example of a cell module used in the present invention. is there.
  • the cell module 10 1 has a tubular electrolyte membrane (perfluorocarbon sulfonic acid resin membrane) 1, the force sword 2 is on the hollow outer surface side of the electrolyte membrane 1, and the anode 3 is the electrolyte membrane. 1 is formed on the hollow inner surface side.
  • a hollow portion (usually a flow path for a fuel gas such as hydrogen gas) 8 through which a reaction gas supplied to the anode 3 flows is formed inside the anode 3.
  • Current collectors 9 and 10 are connected to the force sword 2 and the anode 3, respectively, and one end of the current collectors 9 and 10 functions as an output terminal.
  • a force sword is provided on the outer surface side of the tubular electrolyte membrane, and an anode is provided on the inner surface side.
  • the arrangement of each electrode is not particularly limited, and a force sword is provided on the inner surface side and an anode is provided on the outer surface side. It may be provided.
  • the flow direction of the reaction gas is not particularly limited.
  • FIG. 2 is a partially enlarged sectional view of the cell module shown in FIG.
  • force sword 2 and anode 3 each have a structure in which catalyst layers 4 and 6 and gas diffusion layers 5 and 7 are laminated in order from the electrolyte membrane side.
  • the catalyst layer 4 of force sword 2 consists of three regions 4 a, 4 b, and 4 c with different porosity, and the catalyst layer 4 as a whole has a distribution in which the porosity decreases from the gas diffusion layer 5 side toward the electrolyte membrane 1 side.
  • the porosity of each region is 4 a> 4 b> 4 c.
  • the catalyst layer 6 of the anode 3 is also composed of three regions 6 a, 6 b, and 6 c having different porosities.
  • each region is such that the entire catalyst layer 6 has a porosity from the gas diffusion layer 7 side to the electrolyte membrane 1 side. 6 a> 6 b> 6 c so that the distribution becomes smaller toward the bottom.
  • both the catalyst layer 4 of the force sword 2 and the catalyst layer 6 of the anode 3 have the above-described porosity distribution, but in the present invention, at least of the force sword and the canode It is sufficient that one of them has a porosity distribution in the catalyst layer.
  • the porosity is a ratio of the volume occupied by voids in a unit volume expressed as 100 fraction (%).
  • the fuel cell of the present invention has a distribution in which the porosity of the catalyst layer decreases from the gas diffusion layer side toward the electrolyte membrane side as described above.
  • the diffusibility of the reaction gas can be adjusted by the position in the catalyst layer. That is, on the gas diffusion layer side, since the porosity of the catalyst layer is large and the gas diffusibility is high, a sufficient amount of reaction gas for power generation can be taken from the gas diffusion layer, and the taken reaction gas is taken into the catalyst layer. It is possible to diffuse sufficiently.
  • the diffusion of gas in the catalyst layer on the electrolyte membrane side is restricted, the amount of water carried away by the reaction gas flowing from the catalyst layer and electrolyte membrane on the electrolyte membrane side is reduced. Drying of the electrolyte membrane and the catalyst layer can be prevented. By preventing the electrolyte membrane and the catalyst layer from drying, the power generation performance of the fuel cell is enhanced.
  • the present invention it is possible to prevent the electrolyte membrane and the catalyst layer from being dried while ensuring the supply amount of the reaction gas, and to increase the amount of reaction components that contribute to the electrochemical reaction. It is possible to improve the power generation performance and extend the life of the fuel cell.
  • the porosity of the catalyst layer has a distribution that decreases from the gas diffusion layer side toward the electrolyte membrane side.
  • the force sword catalyst layer has a structure having the above-described porosity distribution, the porosity of the catalyst layer is low on the electrolyte membrane side where drying is desired to be prevented. It shows high water retention, while gas expansion is caused by excess water being pushed out from the electrolyte membrane side. On the dispersion side, the catalyst layer has a high porosity and exhibits high drainage. That is, according to the present invention, it is possible to obtain a fuel cell equipped with a power sword excellent in moisture management ability.
  • the porosity distribution state of the catalyst layer may change stepwise as shown in Fig. 1 if the porosity is smaller on the electrolyte membrane side than on the gas diffusion layer side. It may be good or change with a continuous slope.
  • the catalyst layer is divided into two or five regions equally or non-equally from the gas diffusion layer side to the electrolyte membrane side, and the porosity of each region is determined by gas. It is preferable to set the electrolyte membrane side to be smaller than the diffusion layer side.
  • the distribution state of the porosity may be different between the force sword side and the anode side, or may be the same.
  • the porosity of the catalyst layer is preferably about 80 to 90% in the region in contact with the gas diffusion layer from the viewpoint of gas diffusibility from the gas diffusion layer, while the viewpoint of preventing the electrolyte membrane from drying out Therefore, in the region in contact with the electrolyte membrane, the content is preferably about 60 to 70%. Furthermore, it is usually preferable to adjust the porosity in each region so that the porosity of the entire catalyst layer is about 60 to 90%. For example, in the catalyst layer having a three-stage distribution as shown in Fig. 1, the porosity of 4a and 6a is about 80 to 90%, and the porosity of 4b and 6b is 70 to 80%. The porosity of 4c and 6c is preferably about 60 to 70%.
  • the range of the gas diffusion layer side regions 4a and 6a is from the gas diffusion layer side to 1/3 of the catalyst layer region, and the region 4b 6b range from gas diffusion layer side to catalyst layer thickness 3 It is preferable that the region 4c and 6c on the most electrolyte membrane side from 1/3 to 2/3 is from the gas diffusion layer side to the catalyst layer thickness 2/3 to the electrolyte membrane.
  • the catalyst layer can be formed using an electrode material such as that used in a polymer electrolyte fuel cell, and is usually formed of a catalyst component, a conductive material, and a proton conductive material.
  • the catalyst component is not particularly limited as long as it has a catalytic action for the hydrogen oxidation reaction at the anode and the oxygen reduction reaction in the power sword.
  • platinum Pt
  • ruthenium Ru
  • iridium Ir :
  • rhodium Rh
  • palladium Pd
  • osmium Os
  • tungsten W
  • lead Pb
  • iron Fe
  • Cr chromium
  • cobalt C o
  • Nickel N i
  • Mangan Mn
  • Vanadium V
  • Molybdenum Mo
  • Gallium Ga
  • Aluminum A1
  • platinum and an alloy made of platinum and another metal such as ruthenium.
  • these catalyst components are used by being supported on conductive materials such as carbon materials such as carbonaceous particles and carbonaceous fibers.
  • the fuel cell of the present invention has a cell module having a hollow shape, the electrode area per unit volume can be made larger than that of a fuel cell having a flat cell, so that the catalytic action is not as great as that of platinum. Even if a catalyst component is used, a fuel cell having a high power density per unit volume can be obtained.
  • an electrolyte that can be used as an electrolyte membrane described later can be used.
  • the catalyst layer can be further water-repellent if necessary.
  • Other materials such as a conductive polymer and a binder may be used.
  • the porosity of the catalyst layer may be adjusted as long as the catalyst function, gas diffusibility, conductivity, and proton conductivity in the catalyst layer are not impaired, and the method is not particularly limited.
  • the volume occupied by the entire solid material forming the catalyst layer as described above is different.
  • the solid material for adjusting the volume occupied by the entire solid material forming each region may be only one type, or two or more types, or a catalyst.
  • the volume of the solid material may be adjusted by changing the amount of all the solid materials forming the layer.
  • the material forming the catalyst layer may be different between the regions of the catalyst layer having different porosity.
  • the catalyst layer having regions with different porosities may be formed by using, for example, catalyst pastes having different volume concentrations of solid components or catalyst pastes having different particle sizes of solid components, or laser ablation. It can be produced by forming catalyst layers having different porosities by sol-gel method, sputtering, oxide plating, etc., and laminating them by a method such as transfer.
  • the catalyst component has a distribution in which the amount of the catalyst component per unit volume in the catalyst layer increases from the gas diffusion layer side toward the electrolyte membrane side.
  • the amount of catalyst component is large in the region of the electrolyte membrane with low porosity, the reaction components in the reaction gas with limited diffusion more reliably come into contact with the catalyst and cause a reaction, so hydrogen or oxygen is in the molecular state of the electrolyte. The probability of passing through the membrane Get smaller.
  • the distribution state of the catalyst component in the catalyst layer may be a distribution in which the amount of the catalyst component per unit volume is larger on the electrolyte membrane side than on the gas diffusion layer side, and may change stepwise or continuously. It may change with a certain inclination.
  • the density of the catalyst component may be distributed in the same form as the distribution of the porosity of the catalyst layer. For example, if the porosity of the catalyst layer changes stepwise in three stages as shown in Fig. 1, the amount of catalyst component in the cathode side catalyst layer 4 is 4 a ⁇ 4 b ⁇ 4 c, In the side catalyst layer 6, the amount of the catalyst component may be 6a ⁇ 6b ⁇ 6c.
  • the distribution of the catalyst component amount may be different from the distribution of the porosity of the catalyst layer. Further, the distribution state of the catalyst component amount may be different between the force sword side and the anode side, or may be the same.
  • the amount of catalyst component in the catalyst layer depends on the catalyst component used, it is usually preferred to be about 0.1 to 0.2 mgZcm 2 per unit area for the entire catalyst layer, so the amount of catalyst component for the entire catalyst layer Is preferably distributed in the thickness direction of the catalyst layer (the direction from the electrolyte membrane side to the gas diffusion layer) so that the above is in the above range.
  • the amount of the catalyst component in each region in the thickness direction of the catalyst layer is not particularly limited, but in the region in contact with the electrolyte membrane, about 0.3 to 0.4 mgZ cm 3 per unit volume from the viewpoint of preventing cross leakage. It is preferred to be with. For example, in a catalyst layer with a three-level porosity distribution as shown in Fig.
  • 4 a and 6 a catalyst component amount per unit volume is about 0.05 to 0. l mg / cm 3
  • 4 b and 6 b platinum amount is 0.1 to 0.2 mg / cm 3 per unit volume It is preferable that the amount of platinum of about 4 c and 6 c be about 0.3 to 0.4 mg / cm 3 per unit volume.
  • the catalyst layer can be formed using a catalyst paste in which a catalyst component, a conductive material, a proton conductive material, and other components as necessary are dispersed in a solvent.
  • a catalyst paste C for the regions 4 c and 6 c located closest to the electrolyte membrane in the catalyst layer is prepared.
  • the catalyst paste C can form a catalyst layer having a porosity of 60 to 70% and a catalyst component amount of 0.3 to 0.4 mg / cm 3 per unit volume.
  • This catalyst paste C is divided into three parts, one is used as it is as catalyst paste C for the regions 4 c and 6 c, and the other two have a porosity of 4 a> 4 b> 4 c, 6 a> 6 b> 6 c and the proton conductivity as described above so that the catalyst layers 4 and 6 with the catalyst component amounts of 4 a 4 b ⁇ 4 c, 6 a 6 b 6 c can be formed.
  • catalyst paste B for regions 4b and 6b Dilute with the addition of organic substances, conductive materials, or other components (eg, ethanol, etc.) to obtain catalyst paste B for regions 4b and 6b (porosity 70 to 80%, unit of catalyst components) 0.1 to 0.2 mg Z cm 3 catalyst layer per volume), catalyst paste A for regions 4a and 6a (porosity 80 to 90%, catalyst component amount per unit volume) 0. 5 to 0. lmg no cm 3 of catalyst layer) is prepared.
  • the method for forming the catalyst layers 4 and 6 on the inner and outer surfaces of the tubular electrolyte membrane 1 using the catalyst paste thus obtained is not particularly limited.
  • a tube-shaped electrolyte membrane is prepared, and catalyst paste C is first applied to the inner and outer surfaces of the electrolyte membrane and dried to form catalyst layers in regions 4c and 6c.
  • a solution containing carbonaceous particles and Z or carbonaceous fibers and a water-repellent resin is applied to the regions 4 a and 6 a and dried to form the gas diffusion layers 5 and 7.
  • a cathode are obtained.
  • the catalyst layer 6 and the gas diffusion layer 7 are formed so that the hollow portion 8 exists on the inner surface of the gas diffusion layer 7 formed on the inner surface side of the electrolyte membrane.
  • catalyst pastes C, B, A on the outer surface of the electrolyte membrane layer
  • the catalyst layers of the regions 4 c, 4 b, and 4 a are formed in this order, and a solution containing a carbon material is applied to the outer surface of the region 4 a and dried to form the gas diffusion layer 5.
  • a tubular electrolyte membrane having a force sword 3) is obtained.
  • the solvent used in forming the electrolyte membrane, the catalyst layer, and the gas diffusion layer may be appropriately selected according to the dispersion and Z or the material to be dissolved, and the coating method for forming each layer Also, it can be appropriately selected from various methods such as spraying and screen printing.
  • an electrolyte membrane having a tubular hollow shape is used as the hollow electrolyte membrane.
  • the hollow electrolyte membrane in the present invention is not limited to the tubular shape, and has a hollow portion, and the hollow portion is in the hollow portion. Any reaction component may be used as long as it can supply the reaction components necessary for the electrochemical reaction to the inner surface side electrode by flowing the reaction gas.
  • the perfluorocarbon sulfonic acid resin film which is one of solid polymer electrolyte membranes, which is a kind of proton conducting membrane, is used as the electrolyte membrane.
  • the polymer electrolyte membrane in addition to perfluorocarpone sulfonic acid resin, materials such as those used in electrolyte membranes of polymer electrolyte fuel cells can be used.
  • Solid polymer electrolyte membranes using such electrolytes can be reinforced with perfluorocarbon polymers in the form of fibrils, fabrics, fabrics, and porous sheets, and inorganic oxides or metals on the membrane surface. It can also be captured by coating.
  • perfluorocarbon sulfonic acid resin membranes include commercially available products such as Nafion (trade name) manufactured by DuPont, USA and Flemion (trade name) manufactured by Asahi Glass.
  • the proton conductive electrolyte membrane is not limited to the solid polymer electrolyte membrane as described above, and a proton conductor made by impregnating a porous electrolyte plate with a phosphoric acid aqueous solution or a porous conductor made of porous glass.
  • Hydrogelated phosphate glass, Organic mono-inorganic hybrid proton conductive membrane with proton conductive functional groups introduced into the surface and pores of nano-porous porous glass, inorganic metal fiber reinforced electrolyte polymer Etc. can be used.
  • the method for forming the tubular electrolyte membrane is not particularly limited. An electrolyte membrane formed in a tube shape may be used.
  • a conductive material mainly composed of a carbon material such as carbonaceous particles and / or carbonaceous fibers can be used as the gas diffusion layer.
  • the sizes of the carbonaceous particles and the carbonaceous fibers may be appropriately selected in consideration of the dispersibility in the solution when the gas diffusion layer is produced, the drainage of the obtained gas diffusion layer, and the like.
  • the configuration of the electrodes provided on the inner and outer surfaces of the electrolyte membrane, the materials used for the electrodes, etc. may be the same or different.
  • polytetrafluoroethylene polyvinylidene fluoride (PVDF), perfluoroethylene carbon alkoxy decane, ethylene-tetrafluoroethylene polymer
  • PVDF polyvinylidene fluoride
  • perfluoroethylene carbon alkoxy decane ethylene-tetrafluoroethylene polymer
  • water-repellent treatment by impregnating with a mixture of these materials or by forming a water-repellent layer using these substances.
  • Examples of the tube-like carbonaceous material that includes the carbonaceous particles and / or carbonaceous fibers and is formed into a tube shape include, for example, carbon materials such as carbonaceous particles and epoxy and Z or phenolic materials. It can be obtained by dispersing the resin in a solvent, forming it into a tupe shape, thermosetting, and firing.
  • the inner and outer diameters, length, etc. of the tubular cell module can be designed as appropriate according to the output required for the fuel cell and the design and operating conditions of the fuel cell, such as the equipment to which the fuel cell is applied.
  • the outer diameter of the tubular electrolyte membrane is preferably from 0.1 to 10 mm, more preferably from 0.1 to 1 mm, and from 0.1 to 0.5 mm. Particularly preferred is mm. Outside the tubular electrolyte membrane At present, it is difficult to manufacture a product with a diameter of less than 0.01 mm due to technical problems. On the other hand, a product with an outer diameter of more than 10 mm has a small surface area relative to the occupied volume. This is not preferable because the power generation output per unit volume of the obtained cell module is reduced.
  • Perfluorocarbon sulfonic acid resin membranes are preferred to be thin from the viewpoint of improving the proton conductivity. However, if they are too thin, the function of sequestering gas will be reduced and the permeation rate of non-proton hydrogen will increase. End up. However, compared with the conventional fuel cell in which flat cells for a flat fuel cell are stacked, the fuel cell produced by collecting a large number of hollow cell modules can take up a large electrode area, so it is slightly thicker. Even when a membrane is used, sufficient output is shown. From this viewpoint, the thickness of the perfluorocarbon sulfonic acid resin membrane is 10 to 100 m, more preferably 50 to 60 ⁇ m, and further preferably 50 to 55 m. It is.
  • the preferable range of the inner diameter is from 0.01 to 10 mm, and more preferably from 0.0 :! ⁇ l mm, and more preferably 0.5:! ⁇ 0.5 mm.
  • the thickness of the catalyst layer provided on the inner and outer surfaces of the electrolyte membrane is preferably about 1 to 10 ⁇ , and the thickness of the gas diffusion layer is preferably about 3 to 10 ⁇ .
  • the cell module having a hollow shape used in the fuel cell of the present invention is not limited to the configuration exemplified above, and a layer other than the catalyst layer and the gas diffusion layer may be provided for the purpose of enhancing the function of the cell module. good.
  • the form and material of the current collector (9, 10) are not particularly limited. Examples of the current collector material include a metal wire or foil such as stainless steel.
  • the current collector may be fixed on the electrode with a conductive adhesive such as a strong bonding adhesive or an Ag paste. Les.
  • a perfluorocarbon sulfonic acid resin film which is a proton conducting film, is used as the electrolyte film, but the electrolyte film used in the fuel cell of the present invention is used.
  • the electrolyte film used in the fuel cell of the present invention is used.
  • Examples of other ion-conducting electrolytes such as hydroxide ions and oxide ions (O 2 —) include those containing ceramics.
  • the cell modules having the configuration as shown in FIG. 1 usually form a group of cells that are arrayed and supported by a support plate, and the anode terminals and force sword terminals of each cell module are bundled and connected in parallel.
  • This parallel cell group is connected in series with other cell groups to form a cell assembly, which is surrounded by an exterior member and casing.
  • the reaction gas is supplied to the surface of each electrode.
  • the configuration of the fuel cell such as the cell module and the connection configuration and arrangement configuration of the cell group, is not particularly limited.
  • a cell group in which cell modules are connected in series may be used, or for each cell group. And each internal space thereof may be communicated with a reaction gas supply source.
  • the fuel cell according to the present invention is useful as a fuel cell that is easy to downsize and operates at a low temperature and further improves the power generation performance and extends the life. Yes, especially suitable for use as a portable or mobile power source.

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Abstract

Pile à combustible capable de fournir une quantité suffisante de gaz réactif, d'améliorer le rendement d'utilisation d'un composant réactif contenu dans ledit gaz réactif fourni et de freiner la dessication d'une pellicule d'électrolyte. La pile à combustible comprend une pellicule d'électrolyte de forme creuse et un module de pile pourvu d'une paire d'électrodes disposées sur la surface intérieure et la surface extérieure de la pellicule d'électrolyte. Au moins une des deux électrodes possède une couche de catalyseur et une couche de diffusion de gaz, positionnées dans cet ordre à partir du côté de la pellicule d'électrolyte. Le degré de porosité de la couche de catalyseur est réparti de façon à diminuer en passant du côté de la couche de diffusion de gaz vers le côté de la pellicule d'électrolyte.
PCT/JP2006/302311 2005-02-04 2006-02-03 Pile a combustible Ceased WO2006083038A1 (fr)

Applications Claiming Priority (2)

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JP2005028448A JP2006216404A (ja) 2005-02-04 2005-02-04 燃料電池

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US8206877B2 (en) 2007-11-27 2012-06-26 Toyota Jidosha Kabushiki Kaisha Membrane electrode assembly for fuel cell, fuel cell, and fuel cell system
CN111313061A (zh) * 2020-02-28 2020-06-19 先进储能材料国家工程研究中心有限责任公司 燃料电池膜电极及其制备方法

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JPH0888008A (ja) * 1994-09-19 1996-04-02 Toyota Motor Corp 燃料電池とその製造方法
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JP2002237306A (ja) * 2001-02-08 2002-08-23 Fuji Electric Co Ltd 固体高分子形燃料電池およびその製造方法
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JP2004087267A (ja) * 2002-08-26 2004-03-18 Toyota Motor Corp 燃料電池用電極触媒、その製造方法および製造装置
JP2004111191A (ja) * 2002-09-18 2004-04-08 Toyota Motor Corp 燃料電池用の膜・電極触媒構造体
JP2004319433A (ja) * 2003-03-31 2004-11-11 Seiko Epson Corp 機能性多孔質層の形成方法、燃料電池の製造方法、電子機器および自動車

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JPH03297061A (ja) * 1990-04-17 1991-12-27 Fuji Electric Co Ltd 燃料電池用電極触媒層
JPH0888008A (ja) * 1994-09-19 1996-04-02 Toyota Motor Corp 燃料電池とその製造方法
JP2002124273A (ja) * 2000-10-18 2002-04-26 Mitsubishi Rayon Co Ltd 固体高分子型燃料電池とその製造方法及び固体高分子型燃料電池モジュール
JP2002237306A (ja) * 2001-02-08 2002-08-23 Fuji Electric Co Ltd 固体高分子形燃料電池およびその製造方法
US20040001988A1 (en) * 2002-06-28 2004-01-01 Graftech Inc. Perforated cylindrical fuel cells
JP2004087267A (ja) * 2002-08-26 2004-03-18 Toyota Motor Corp 燃料電池用電極触媒、その製造方法および製造装置
JP2004111191A (ja) * 2002-09-18 2004-04-08 Toyota Motor Corp 燃料電池用の膜・電極触媒構造体
JP2004319433A (ja) * 2003-03-31 2004-11-11 Seiko Epson Corp 機能性多孔質層の形成方法、燃料電池の製造方法、電子機器および自動車

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8206877B2 (en) 2007-11-27 2012-06-26 Toyota Jidosha Kabushiki Kaisha Membrane electrode assembly for fuel cell, fuel cell, and fuel cell system
CN111313061A (zh) * 2020-02-28 2020-06-19 先进储能材料国家工程研究中心有限责任公司 燃料电池膜电极及其制备方法

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