WO2019139415A1 - Couche de diffusion de gaz destinée à une pile à combustible, ensemble membrane-électrode la comprenant, pile à combustible la comprenant, et procédé de préparation d'une couche de diffusion de gaz destinée à une pile à combustible - Google Patents

Couche de diffusion de gaz destinée à une pile à combustible, ensemble membrane-électrode la comprenant, pile à combustible la comprenant, et procédé de préparation d'une couche de diffusion de gaz destinée à une pile à combustible Download PDF

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WO2019139415A1
WO2019139415A1 PCT/KR2019/000476 KR2019000476W WO2019139415A1 WO 2019139415 A1 WO2019139415 A1 WO 2019139415A1 KR 2019000476 W KR2019000476 W KR 2019000476W WO 2019139415 A1 WO2019139415 A1 WO 2019139415A1
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layer pattern
porous layer
fuel cell
gas diffusion
diffusion layer
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PCT/KR2019/000476
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English (en)
Korean (ko)
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오근환
김도영
조현아
김혁
양재춘
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주식회사 엘지화학
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Publication of WO2019139415A1 publication Critical patent/WO2019139415A1/fr

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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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • 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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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 gas diffusion layer for a fuel cell, a membrane-electrode assembly comprising the same, a fuel cell including the same, and a method of manufacturing a gas diffusion layer for a fuel cell.
  • a fuel cell is a device that produces electrical energy by electrochemically reacting fuel and oxygen.
  • a polymer electrolyte membrane PEM
  • phosphoric acid type a phosphoric acid type
  • molten carbonate type a molten carbonate type
  • solid oxide type oxide a solid oxide type oxide
  • alkaline aqueous solution type a polymer electrolyte membrane
  • a polymer electrolyte membrane fuel cell has a low operating temperature and high efficiency, a high current density and a high output density, a short start-up time , There is a rapid response to load change.
  • the polymer electrolyte fuel cell can be divided into a methanol solution, a direct methanol fuel cell using air as fuel, and a hydrogen fuel cell using hydrogen and air as fuel.
  • the structure of the polymer electrolyte fuel cell includes a catalyst layer on each gas diffusion layer And a membrane electrode assembly (MEA) having a gas diffusion electrode bonded to the coated fuel electrode and an air electrode bonded to each other, and a gasket for preventing the outflow of gas from the edge of the gas diffusion electrode.
  • MEA membrane electrode assembly
  • the gas diffusion layer is formed by coating a microporous layer (MPL) on a carbon substrate made of a porous carbon film.
  • the ion exchange membrane of the polymer electrolyte fuel cell has a property of conducting hydrogen ions in proportion to the water content. Therefore, humidified feed gas is used to increase the ionic conductivity, and since the product in the fuel cell is water, proper water management in the fuel cell prevents water from flooding the reaction gas passage, ) Phenomenon occurs. Therefore, it is necessary to research and develop measures to appropriately manage the water in the fuel cell.
  • the gas diffusion layer is a component that effectively controls the water in the polymer electrolyte fuel cell, and the water management ability in the fuel cell is changed according to the structure of the gas diffusion layer.
  • the water management ability of the gas diffusion layer is a polymer electrolyte type It is closely related to the performance of the fuel cell.
  • Patent Document 1 United States Patent No. 8372557 B2
  • the present invention provides a gas diffusion layer for a fuel cell, a membrane-electrode assembly including the same, a fuel cell including the same, and a method for manufacturing a gas diffusion layer for a fuel cell.
  • the present disclosure relates to a carbon support; And a pore layer disposed on the carbon support, wherein the pore layer comprises a first pore layer pattern and a second pore layer pattern, wherein each of the second pore layer patterns comprises a first pore layer pattern of the pore layer And the porosity of the first porous layer pattern is larger than the porosity of the second porous layer pattern.
  • the present disclosure also relates to a cathode comprising: a cathode; Anode; And a polymer electrolyte membrane provided between the cathode and the anode, wherein at least one of the cathode and the anode includes the above-described gas diffusion layer for a fuel cell.
  • the present disclosure also relates to a stack comprising two or more of the above-described membrane-electrode assemblies, and a separator provided between the membrane-electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply part for supplying the oxidant to the stack.
  • the present invention also relates to a method of manufacturing a carbon nanotube, comprising: forming a first porous layer pattern by applying a first porous layer pattern composition on a carbon support; And forming a second porous layer pattern by applying a second porous layer pattern composition on a part or the entire surface of the carbon support on which the first porous layer pattern is not formed .
  • the gas diffusion layer for a fuel cell has a region optimized for supplying oxygen and a region capable of discharging water at the same time so that fuel supply is facilitated and water discharge power over the entire gas diffusion layer .
  • a gas diffusion layer for a fuel cell is manufactured using the manufacturing method of a gas diffusion layer for a fuel cell according to an embodiment of the present invention, a gas diffusion layer is formed by using a printing method. Therefore, Is easily formed.
  • the gas diffusion layer for a fuel cell is manufactured using the manufacturing method of a gas diffusion layer for a fuel cell according to an embodiment of the present invention, a gas diffusion layer is formed by using a printing method, It is easy.
  • FIG. 3 shows the results of the performance test at the relative humidity of 50 RH% in Experimental Example 2.
  • FIG. 5 schematically shows a method of manufacturing a gas diffusion layer for a fuel cell according to an embodiment of the present invention.
  • FIG. 6 shows a membrane-electrode assembly according to one embodiment of the present disclosure.
  • FIG. 7 shows a fuel cell according to an embodiment of the present invention.
  • Fig. 9 is a schematic diagram showing the electricity generation principle of the fuel cell.
  • FIG. 10 is a cross-sectional view of the membrane-electrode assembly of Examples 4 to 6.
  • FIG. 10 is a cross-sectional view of the membrane-electrode assembly of Examples 4 to 6.
  • a member When a member is referred to herein as being “on " another member, it includes not only a member in contact with another member but also another member between the two members.
  • the term "layer” means that at least 70% of the area in which the layer is present is covered. , Preferably at least 75%, more preferably at least 80%.
  • the present disclosure relates to a carbon support; And a pore layer disposed on the carbon support, wherein the pore layer comprises a first pore layer pattern and a second pore layer pattern, wherein each of the second pore layer patterns comprises a first pore layer pattern of the pore layer And the porosity of the first porous layer pattern is larger than the porosity of the second porous layer pattern.
  • the gas diffusion layer for a fuel cell serves to transfer hydrogen and oxygen, which are fuel, to the catalyst layer, and discharges water generated in the cathode to the outside.
  • excessive water is discharged, so that it is not possible to sufficiently supply water to the electrolyte membrane under low humidification conditions.
  • the laminate structure gas diffusion layer when the pore layers having different porosity from each other are sequentially stacked in the vertical direction of the carbon support (hereinafter, the laminate structure gas diffusion layer), different functions of the respective pore layers can not be effectively performed. Therefore, there is a problem that performance is lowered when the laminated structure gas diffusion layer is applied to a fuel cell (Comparative Example 1 and Comparative Example 2).
  • the multilayered gas diffusion layer has a long length in the thickness direction, and it takes a long time for the fuel gas to permeate to reach the catalyst layer, thereby increasing the permeation resistance and also raising the production cost.
  • a pore layer having a different porosity is introduced into one pore layer so that the water generated in the cathode is well discharged through the first pore layer pattern, and the movement of the material gas through the second pore layer pattern Smoothness was achieved.
  • the porosity of the first pore layer pattern may be greater than the porosity of the second pore layer pattern.
  • the first porous layer pattern discharges water well, while the second porous layer pattern can effectively disperse hydrogen or oxygen, which is a fuel gas, into the catalyst layer evenly without discharging water well.
  • the porosity of the first porous layer pattern is increased to prevent the flooding that may be caused by the liquid material by discharging the liquid material (H 2 O) generated in the cathode well.
  • the porosity of the second porous layer pattern was reduced, and the discharge of the liquid material (H 2 O) generated in the cathode was suppressed. In this case, there is an effect that the phenomenon that the liquid material is discharged by the pores of the second porous layer pattern to block the pores is suppressed, and the fuel can move well through the pores.
  • the first porous layer pattern may be referred to as a " water exhaust porous layer "and the second porous layer pattern may be referred to as a" fuel gas permeable porous layer ".
  • the function and performance are not limited to the above-mentioned designations, and the function of the first porous layer pattern and the function of the second porous layer pattern can be distinguished.
  • each of the second pore layer patterns may be included in a part or all of a region where the first pore layer pattern of the pore layer is not provided. This means that each of the second pore layer patterns is provided only in a region where the first pore layer pattern of the pore layer is not provided.
  • Each of the pore layer patterns has a single layer structure and does not have a laminate structure. This can mean that when an arbitrary straight line is drawn in a direction perpendicular to the surface of the carbon support from any point of the second pore layer pattern, the straight line does not meet with the first pore layer pattern.
  • the pore layer has a single layer structure, and the first pore layer pattern and the second pore layer pattern may be included in the single layer structure.
  • the pore layer may include at least two first pore layer patterns and at least two second pore layer patterns.
  • the line width of the first pore layer pattern may be 100 ⁇ ⁇ or more and 2 mm or less, preferably 300 ⁇ ⁇ or more and 1.5 mm or less, more preferably 400 ⁇ ⁇ or more or 1 mm or less.
  • the high porosity of the first porous layer pattern can be easily achieved, thereby maximizing the effect of discharging water by the first porous layer pattern.
  • the line width of the second pore layer pattern may be 100 ⁇ ⁇ or more and 2 mm or less, preferably 300 ⁇ ⁇ or more and 1.5 mm or less, and more preferably 400 ⁇ ⁇ or more and 1 mm or less.
  • the numerical range is satisfied, the effect of discharging water on the second porous layer pattern is suppressed, and the fuel can be effectively delivered.
  • the line widths of the first porous layer pattern and the second porous layer pattern may be the same.
  • the function of the gas diffusion layer can be enhanced by balancing the water discharge effect by the first pore layer pattern and the material gas supply effect by the second pore layer pattern.
  • the linewidths of the first and second pore layer patterns may be controlled by the number of coatings of the pore layer pattern composition coated to form each pore layer pattern. For example, in order to form a pore layer pattern having a line width of 1 ⁇ ⁇ , a 1 ⁇ ⁇ pore layer pattern can be formed by one coating, and a pore layer pattern having a line width of 0.5 ⁇ ⁇ is formed twice to obtain a total line width of 1 Mu m can be formed.
  • the line widths of the first porous layer pattern and the second porous layer pattern can be measured by analyzing the surface of the porous layer of the gas diffusion layer through an SEM photograph or an optical microscope photograph.
  • the line width of the first porous layer pattern or the second porous layer pattern may be a value measured several times and averaged.
  • Fig. 8 it may mean the shortest length in a cross section perpendicular to the thickness direction of each pattern.
  • the line width of the pattern can be measured by an optical microscope or an SEM photograph.
  • the method of measuring the line width of such a pattern can be applied not only to the case where the shape of the pattern is linear, but also to the case of circular or polygonal.
  • the 'longitudinal direction of the pattern' may mean the 'longitudinal direction of a circular arc of the pattern'.
  • the 'longitudinal direction of the pattern' may mean 'the longitudinal direction of any side of the pattern'.
  • the line width may mean the shortest length in a cross section perpendicular to the longitudinal direction of either side of the triangle.
  • the average size of the pores of the first porous layer pattern may be 50 ⁇ m to 100 ⁇ m, preferably 55 ⁇ m to 90 ⁇ m, more preferably 60 ⁇ m to 80 ⁇ m.
  • the average size of the pores of the second pore layer pattern may be 10 ⁇ m to 60 ⁇ m, preferably 20 ⁇ m to 55 ⁇ m, more preferably 30 ⁇ m to 50 ⁇ m.
  • the first porous layer pattern discharges water well and the second porous layer pattern does not discharge water well Hydrogen or oxygen as a fuel gas can be dispersed evenly in the catalyst layer.
  • the porosity of the first porous layer pattern may be 30% to 90%, preferably 40% to 90%, more preferably 70% to 90%.
  • the porosity of the second porous layer pattern may be 10% to 80%, preferably 30% to 70%, more preferably 30% to 50%.
  • the porosity of the first porous layer pattern and the second porous layer pattern satisfies the above numerical value range, the water discharge effect of the first porous layer pattern is maximized and the water discharge effect of the second porous layer pattern is reduced So that the fuel gas can be easily transferred through the pores of the second porous layer.
  • the porosity of the pores of the first porous layer pattern and the second porous layer pattern and the average size of the pores can be measured by a method well known in the field to which this technique belongs.
  • MIP Mercury Intrusion Porosimetry
  • the size of two or more pores can be measured And then averaged and converted into the average size.
  • the thicknesses of the first porous layer pattern and the second porous layer pattern are equal to or different from each other, and may be 5 [mu] m to 50 [mu] m, respectively.
  • the difference in thickness between the first pore layer pattern and the second pore layer pattern may be 1 ⁇ or less, preferably 0.5 ⁇ or less, more preferably 0.1 ⁇ or less.
  • the lower limit may be 0 ⁇ ⁇ . That is, it may be 0 ⁇ or more and 1 ⁇ or less, preferably 0 ⁇ or more and 0.5 ⁇ or less, more preferably 0 ⁇ or more and 0.1 ⁇ or less.
  • the first porous layer pattern and the second porous layer pattern are formed in a single layer, so that the water discharge effect by the first porous layer pattern and the hydrogen gas or the oxygen Can be well dispersed evenly in the catalyst layer.
  • the thickness of the pore layer pattern can be measured through a scanning electron microscope (SEM) of the gas diffusion layer.
  • the thickness of the carbon support may be between 150 ⁇ m and 250 ⁇ m.
  • the area in which the first porous layer pattern and the carbon support contact with each other is 40% or more and less than 100%, preferably 40% or more and 80% or less, 50% or more and 70% or less.
  • the numerical range is satisfied, the effect of discharging the water through the first porous layer pattern can be easily achieved.
  • the above area can be measured by analyzing an SEM photograph of a gas diffusion layer for a fuel cell. Specifically, it may be a value calculated by dividing the entire area of the carbon support with respect to the area occupied by the first porous layer pattern in the SEM photograph of the surface of the gas diffusion layer, and may be an average value of values obtained by repeating the calculation process several times.
  • the shapes of the first porous layer pattern and the second porous layer pattern may be the same or different from each other, and may be independently one or two or more types selected from the group consisting of linear, Lt; / RTI >
  • the shape of each of the pore layer patterns means a shape of a cross section in the horizontal direction of each pattern.
  • the shapes of the first porous layer pattern and the second porous layer pattern may be adjusted through a printing pattern input method.
  • the printing pattern input method may be a method of storing a desired shape as a computer picture file.
  • the shapes of the first porous layer pattern and the second porous layer pattern may be other than linear, circular, and polygonal shapes described above as long as the respective patterns do not overlap with each other.
  • the average size and porosity of the pores of the first and second pore layer patterns described above can be controlled by changing the kind of carbon material contained in each pattern.
  • the first porous layer pattern may include at least one carbon material selected from the group consisting of spherical carbon, carbon nanotube (CNT), and carbon nanofibers (CNF).
  • the first porous layer pattern may include carbon nanotubes (CNTs), and may further include at least one carbon material selected from the group consisting of spherical carbon and carbon nanofibers (CNT) have.
  • the porosity of the first pore layer pattern may be adjusted by including the carbon nanotube (CNT) in the first pore layer pattern. This is due to the geometry of the carbon nanotubes (CNTs).
  • the second pore layer pattern may comprise at least one carbon material selected from the group consisting of spherical carbon materials, fullerene and graphene.
  • the first porous layer pattern and the second porous layer pattern may each comprise Teflon.
  • the carbon support may be any conventional material known in the art, but may be, for example, carbon paper, carbon cloth or carbon felt, May be preferably used, but are not limited thereto.
  • the present disclosure includes a cathode; Anode; And a polymer electrolyte membrane provided between the cathode and the anode, wherein at least one of the cathode and the anode includes the above-described gas diffusion layer for a fuel cell.
  • the cathode or the anode of the membrane-electrode assembly of the present invention includes the above-described gas diffusion layer for a fuel cell, so that performance can be improved.
  • the cathode and the anode may include a catalyst layer for a fuel cell. That is, the cathode includes a cathode catalyst layer, and the anode may include an anode catalyst layer.
  • the catalyst layer for a fuel cell may be manufactured by a conventional method known in the art, for example, by coating a catalyst composition on the gas diffusion layer for a fuel cell and drying the same . At this time, a plurality of catalyst layers may be formed by sequentially coating and drying the catalyst composition having different ionomer contents.
  • Examples of the method of applying the catalyst composition on the gas diffusion layer include printing, tape casting, bar casting, slot die casting, spraying, rolling, But are not limited to, methods such as blade coating, spin coating, inkjet coating, and brushing. In addition, coating can be performed using an inkjet apparatus.
  • the hydrogen ion transfer resistance of at least one of the cathode catalyst layer and the anode catalyst layer is 0.2 ⁇ cm 2 or less, 0.1 ⁇ cm 2 or less, and preferably 0.05 ⁇ cm 2 or less.
  • the hydrogen ion transfer resistance of the catalyst layer is preferably as low as possible, and therefore the lower limit thereof is not particularly limited.
  • the ohmic resistance of the membrane-electrode assembly may be 200 m? Cm 2 , preferably 100 m? Cm 2 or less, more preferably 70 m? Cm 2 or less. In this case, the performance of the membrane-electrode assembly itself is improved.
  • the ohmic resistance of the membrane-electrode assembly can be achieved by manufacturing the cathode catalyst layer or the anode catalyst layer of the membrane-electrode assembly with the above-described catalyst composition for a fuel cell.
  • the hydrogen ion conductivity () of the catalyst layer can be calculated by the following equation (1).
  • R is the hydrogen ion transfer resistance of the catalyst layer
  • t is the average thickness of the catalyst layer
  • A is the area of the catalyst layer.
  • the hydrogen ion conductivity of the catalyst layer may be 0.02 mS cm -1 or more, specifically 0.03 mS cm -1 or more. In this case, there is an advantage that the utilization rate of the catalyst can be improved by the smooth hydrogen ion transmission.
  • the catalyst layer may have an average thickness of 3 ⁇ or more and 15 ⁇ or less, specifically 0.3 mgPt / cm 2 (0.3 mg of Pt per 1 cm 2 of the reference area) It may be 5 ⁇ ⁇ or more and 12 ⁇ ⁇ or less. In this case, there is an advantage that proper pores and hydrogen ion conductivity can be ensured.
  • the electrolyte membrane may be a polymer electrolyte membrane.
  • the polymer electrolyte membrane is provided between the cathode catalyst layer and the anode catalyst layer, and the polymer contained in the polymer electrolyte membrane may be an ion conductive polymer.
  • the ion conductive polymer may be a hydrocarbon-based polymer, a partially fluorinated polymer, or a fluorinated polymer.
  • the polymer electrolyte membrane may be a hydrocarbon-based polymer electrolyte membrane or a fluorine-based polymer electrolyte membrane.
  • the hydrocarbon-based polymer may be a hydrocarbon-based sulfonated polymer having no fluorine group
  • the fluorinated polymer may be a sulfonated polymer saturated with a fluorine group
  • the partially fluorinated polymer may be a sulfonated polymer that is not saturated with a fluorine group.
  • the ion conductive polymer may be at least one selected from the group consisting of a perfluorosulfonic acid polymer, a hydrocarbon polymer, an aromatic sulfonic polymer, an aromatic ketone polymer, a polybenzimidazole polymer, a polystyrene polymer, A polyimide polymer, a polyimide polymer, a polyvinylidene fluoride polymer, a polyether sulfone polymer, a polyphenylene sulfide polymer, a polyphenylene oxide polymer, a polyphosphazene polymer, a polyethylene naphthalate polymer, a polyester polymer, One or two selected from the group consisting of doped polybenzimidazole-based polymers, polyether ketone-based polymers, polyetheretherketone-based polymers, polyphenylquinoxaline-based polymers, polysulfone-based polymers, polypyrrole-based poly
  • the polymer may be sulfonated and may be a single copolymer, an alternating copolymer, a random copolymer, a block copolymer, a multi-block copolymer or a graft copolymer, but is not limited thereto.
  • the polymer electrolyte membrane when the polymer electrolyte membrane comprises a hydrocarbon-based polymer, it may be a hydrocarbon-based polymer that is a block copolymer including a hydrophilic block and a hydrophobic block.
  • the average thickness of the polymer electrolyte membrane may be 1 ⁇ or more and 100 ⁇ or less.
  • the cathode comprises a cathode catalyst layer
  • the cathode catalyst layer may comprise a catalyst selected from the group consisting of platinum and platinum-transition metal alloys.
  • the anode comprises an anode catalyst layer
  • the catalyst layer of the anode electrode is selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum- ≪ / RTI >
  • the gas diffusion layer included in the cathode may be provided on a surface facing the cathode catalyst layer.
  • the gas diffusion layer included in the anode may be provided on a surface facing the anode catalyst layer.
  • the present specification discloses a stack comprising two or more of the above-described membrane-electrode assemblies, and a separator provided between the membrane-electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply part for supplying the oxidant to the stack.
  • FIG. 9 schematically shows an electricity generation principle of a fuel cell.
  • the most basic unit for generating electricity is a membrane electrode assembly (MEA), which includes an electrolyte membrane M and an electrolyte membrane M, And an anode (A) and a cathode (C) formed on both sides of the cathode (C).
  • MEA membrane electrode assembly
  • F hydrogen
  • H + hydrogen
  • the hydrogen ions move to the cathode C through the electrolyte membrane M.
  • the hydrogen ions transferred through the electrolyte membrane (M) react with the oxidizing agent (O) such as oxygen, and water (W) is produced. This reaction causes electrons to migrate to the external circuit.
  • the membrane electrode assembly may include an electrolyte membrane 10 and a cathode 50 and an anode 51 positioned opposite to each other with the electrolyte membrane 10 interposed therebetween.
  • the cathode includes a cathode catalyst layer 20 and a cathode gas diffusion layer 30 sequentially provided from the electrolyte membrane 10
  • the anode includes an anode catalyst layer 21 and an anode catalyst layer 21 sequentially provided from the electrolyte membrane 10, And a gas diffusion layer 31.
  • the fuel cell may be formed using materials and methods known in the art. Referring to FIG. 7, the fuel cell includes a stack 60, a fuel supply unit 80, and an oxidant supply unit 70.
  • the stack 60 includes one or more membrane-electrode assemblies (MEAs) and, when two or more membrane-electrode assemblies are included, a separator interposed therebetween.
  • the separators are electrically connected to the membrane- And to transfer the fuel and the oxidant supplied from the outside to the membrane electrode assembly.
  • the fuel supply unit 80 serves to supply fuel to the stack and includes a fuel tank 81 for storing the fuel and a pump 82 for supplying the fuel stored in the fuel tank 81 to the stack 60 .
  • a fuel tank 81 for storing the fuel
  • a pump 82 for supplying the fuel stored in the fuel tank 81 to the stack 60 .
  • the fuel gas or liquid hydrogen or hydrocarbon fuel may be used.
  • the hydrocarbon fuel include methanol, ethanol, propanol, butanol or natural gas.
  • the oxidant supply part 70 serves to supply an oxidant to the stack.
  • oxygen is typically used, and oxygen or air can be injected into the pump 82 for use.
  • the stack comprises two or more membrane-electrode assemblies of the present disclosure and, if two or more membrane-electrode assemblies are included, a separator is interposed therebetween.
  • the separation membrane prevents the membrane-electrode assemblies from being electrically connected to each other and transmits the fuel and the oxidant supplied from the outside to the membrane-electrode assembly.
  • the fuel supply part serves to supply fuel to the stack, and may be constituted by a fuel tank for storing the fuel and a pump for supplying the fuel stored in the fuel tank to the stack.
  • the fuel may be hydrogen or hydrocarbon fuel in a gaseous or liquid state, and examples of the hydrocarbon fuel include methanol, ethanol, propanol, or butanol.
  • the oxidant supply part serves to supply the oxidant to the stack.
  • An example of the oxidizing agent is oxygen.
  • the present disclosure relates to a method of forming a porous layer pattern, comprising: applying a first porous layer pattern composition on a carbon support to form a first porous layer pattern; And forming a second porous layer pattern by applying a second porous layer pattern composition on a part or the entire surface of the carbon support on which the first porous layer pattern is not formed .
  • a first porous layer pattern is formed on the carbon support, and a second porous layer pattern is formed on the portion where the first porous layer pattern is not formed.
  • the step of forming the first porous layer pattern and the step of forming the second porous layer pattern can be performed at different points of time.
  • another pore layer pattern is formed on the surface of the carbon support on which the pore layer pattern is not provided, so that the pore layer patterns do not overlap each other.
  • the second porous layer pattern can be selectively formed on a part or the entire surface of the carbon support on which the first porous layer pattern is not formed.
  • each composition is applied by a printing method in order to selectively form each pore layer pattern as described above.
  • the printing method there is an advantage that each pore layer pattern can be formed selectively in a short time.
  • the first porous layer pattern composition and the second porous layer pattern composition are coated by the same or different methods selected from the group consisting of a printing method, a spray coating method and a slot die coating method And may be by any one method selected.
  • the step of forming the first porous layer pattern may further include drying the first porous layer pattern composition.
  • the step of drying the first porous layer pattern composition may be performed at a performance temperature of 25 ° C or higher and 400 ° C or lower, specifically, at room temperature (25 ° C).
  • a performance temperature of 25 ° C or higher and 400 ° C or lower, specifically, at room temperature (25 ° C).
  • the pore size and the porosity of the first porous layer pattern can be controlled to be high.
  • the step of forming the second porous layer pattern may further include drying the second porous layer pattern composition.
  • the step of drying the second porous layer pattern composition may be performed at a performance temperature of 25 ° C or higher and 400 ° C or lower, specifically, at room temperature (25 ° C).
  • a performance temperature of 25 ° C or higher and 400 ° C or lower, specifically, at room temperature (25 ° C).
  • the step of forming the first porous layer pattern may further include a step of heat treating the first porous layer pattern.
  • the step of forming the first porous layer pattern may further include a step of heat treating the second porous layer pattern.
  • the first porous layer pattern composition and the second porous layer pattern composition may further comprise a solvent selected from the group consisting of distilled water, 1-propanol, 2-propanol and propylene glycol.
  • spherical carbon 0.1 g of carbon nanotubes and 0.5 g of Teflon dispersion were placed in a mixed solvent of 3 g of 1-propanol and 12 g of distilled water and ball-milled at a speed of 400 rpm for 2 Lt; / RTI > for 1 hour to prepare a first pore layer pattern composition.
  • a gas diffusion layer for a fuel cell was prepared using the first porous layer pattern composition and the second porous layer pattern composition prepared in the above Production Example.
  • the first porous layer pattern composition was coated on the carbon paper using an inkjet apparatus so as to have a line width of 1 mm each to form two or more first porous layer patterns and the solvent of the composition was dried at room temperature for 10 minutes to 30 minutes . At this time, the interval between the first porous layer patterns was 1 mm.
  • a second pore layer pattern composition was coated between the first pore layer patterns on the carbon paper using an inkjet apparatus to form a second pore layer pattern, and the solvent of the composition was dried.
  • the line width of the second porous layer pattern was 1 mm, and the shapes of the first porous layer pattern and the second porous layer pattern were linear, and were arranged in parallel to each other.
  • a gas diffusion layer for a fuel cell was prepared in the same manner as in Example 1 except that the line width of the first porous layer pattern and the second porous layer pattern was 0.5 mm.
  • a gas diffusion layer for a fuel cell was prepared in the same manner as in Example 1 except that the line width of the first porous layer pattern and the second porous layer pattern was 5 mm.
  • the first porous layer pattern composition is first cast on a carbon paper.
  • the solvent of the composition was dried at room temperature for 10 minutes to 30 minutes to form a first porous layer pattern.
  • the second porous layer pattern composition was cast on the first porous layer pattern, and the solvent of the second porous layer pattern composition was dried to form a second porous layer pattern. That is, a gas diffusion layer having a structure in which carbon paper, a first porous layer pattern and a second porous layer pattern were sequentially laminated was prepared.
  • a membrane-electrode assembly was prepared using the prepared gas diffusion layer.
  • the polymer electrolyte membrane was placed between the anode catalyst layer and the cathode catalyst layer and thermocompression was performed at 140 ⁇ and 10 MPa for 5 minutes to prepare a membrane in which the catalyst layer was transferred. Thereafter, the gas diffusion layer of Example 1 was placed on the catalyst layer of the membrane to which the catalyst layer was transferred, and the cell was tightened at a torque of 45 kgf / cm 2 to prepare a final membrane-electrode assembly.
  • a membrane-electrode assembly was prepared in the same manner as in Example 4 except that the gas diffusion layer of Example 2 was used in place of the gas diffusion layer of Example 1.
  • a membrane-electrode assembly was prepared in the same manner as in Example 4 except that the gas diffusion layer of Example 3 was used instead of the gas diffusion layer of Example 1.
  • FIG. 10 is a SEM cross-sectional photograph of the membrane-electrode assembly of Examples 4 to 6.
  • FIG. 10 it can be confirmed that the difference in thickness (height) between the first porous layer pattern and the second porous layer pattern of the gas diffusion layer is 0 ⁇ ⁇ , which is almost equal.
  • a membrane-electrode assembly was prepared in the same manner as in Example 4 except that the gas diffusion layer according to Comparative Example 1 was used instead of the gas diffusion layer of Example 1.
  • a membrane-electrode assembly was prepared in the same manner as in Example 4 except that a gas diffusion layer (trade name: 39BC, manufactured by SGL Corporation) instead of the gas diffusion layer according to Example 1 was used. Since the gas diffusion layer used in Comparative Example 3 has a structure having a single pore layer pattern, it differs from the gas diffusion layer used in Example 4 having two different types of patterns.
  • a gas diffusion layer trade name: 39BC, manufactured by SGL Corporation
  • Experimental Example 1 was carried out in order to confirm that the fourth embodiment in which the gas diffusion layers have different patterns in a single layer exhibits an excellent structural effect as compared with the gas diffusion layer in the lamination type.
  • the performance of the membrane-electrode assembly was measured using a fuel cell to which the membrane-electrode assembly according to Example 4 and Comparative Example 2 was applied.
  • the temperature of the fuel cell was 70 ⁇ and the relative humidity was 50% RH or 32% RH based on the outlet of the humidifier.
  • the reactant flow rate was 1.5 eq as the fuel electrode and 2.0 eq as the oxidant electrode, respectively.
  • the performance according to the change of the current intensity and the relative humidity was measured.
  • the measured results are shown in Table 1 below, and the I-V characteristics are compared with each other as shown in FIG. 1 and FIG. 1 shows the results of a performance test at a relative humidity of 50 RH% and FIG. 2 at a relative humidity of 32 RH%.
  • the film according to the - means that the performance when compared in the electrode assembly measures the voltage under each @ 600mA / cm 2, @ 1000mA / cm 2 @ under 600mA / cm 2 It was confirmed that the membrane-electrode assembly according to Example 4 was superior to the membrane-electrode assembly according to Comparative Example 2 in measuring the voltage. This is because the fuel diffusion performance of the gas diffusion layer of the membrane-electrode assembly according to Example 4, in which the gas diffusion layers having different performance were separately provided, was superior to that of Comparative Example 2 in which the gas diffusion layers were laminated.
  • the first porous layer pattern having excellent water-dripping effect exhibited excellent water- This is because the fuel gas is smoothly delivered by the second porous layer pattern having excellent performance.
  • the gas diffusion layer according to the present invention when applied to a fuel cell, the performance of a stable membrane-electrode assembly can be manifested under various humidifying conditions, and durability is improved.
  • FIGS. 3 and 4 show performance tests of the fuel cell using the membrane-electrode assembly in Examples 4 to 6 and Comparative Example 3.
  • FIG. in the figure, reference numeral 39BC denotes a fuel cell using the membrane-electrode assembly of Comparative Example 3, wherein the 1 mm pattern corresponds to Example 4, the 0.5 mm pattern corresponds to Example 5, and the 5 mm corresponds to the gas diffusion layer included in the membrane- Quot; means the length of the line width of each pore layer pattern.
  • FIG. 3 shows the test results under the conditions of relative humidity RH 50%
  • FIG. 4 shows the test results under the conditions of relative humidity RH 32%.
  • Example 4 (1 mm) and Example 5 (0.5 mm) in which the line width of the pattern of the gas diffusion layer is 2 mm or less, the IV characteristic (5 mm) It was confirmed that this excellent effect was obtained.
  • the NALCERTEC fuel cell evaluation system was used.

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

Abstract

La présente invention concerne une couche de diffusion de gaz destinée à une pile à combustible, la couche de diffusion de gaz comprenant : un support de carbone ; et une couche poreuse située sur le support de carbone, la couche poreuse comprenant un premier motif de couche poreuse et un second motif de couche poreuse, le second motif de couche poreuse étant compris dans une partie ou la totalité d'une région dans laquelle le premier motif de couche poreuse de la couche poreuse n'est pas fourni, et la porosité du premier motif de couche poreuse étant supérieure à celle du second motif de couche poreuse, un ensemble membrane-électrode la comprenant, une pile à combustible la comprenant, et un procédé de préparation d'une couche de diffusion de gaz destinée à une pile à combustible.
PCT/KR2019/000476 2018-01-12 2019-01-11 Couche de diffusion de gaz destinée à une pile à combustible, ensemble membrane-électrode la comprenant, pile à combustible la comprenant, et procédé de préparation d'une couche de diffusion de gaz destinée à une pile à combustible WO2019139415A1 (fr)

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