WO2017175892A1 - Membrane électrolytique composite pour pile à combustible, ensemble membrane-électrodes comportant une telle membrane, pile à combustible comportant un tel ensemble, et procédé pour la fabrication de membrane électrolytique composite pour pile à combustible, d'ensemble membrane-électrodes comportant une telle membrane, de pile à combustible comportant un tel ensemble - Google Patents

Membrane électrolytique composite pour pile à combustible, ensemble membrane-électrodes comportant une telle membrane, pile à combustible comportant un tel ensemble, et procédé pour la fabrication de membrane électrolytique composite pour pile à combustible, d'ensemble membrane-électrodes comportant une telle membrane, de pile à combustible comportant un tel ensemble Download PDF

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WO2017175892A1
WO2017175892A1 PCT/KR2016/003556 KR2016003556W WO2017175892A1 WO 2017175892 A1 WO2017175892 A1 WO 2017175892A1 KR 2016003556 W KR2016003556 W KR 2016003556W WO 2017175892 A1 WO2017175892 A1 WO 2017175892A1
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fuel cell
electrolyte membrane
composite electrolyte
porous support
ptfe
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PCT/KR2016/003556
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English (en)
Korean (ko)
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정지홍
정성기
서영균
권정오
양연화
양의석
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(주)상아프론테크
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • 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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/109—After-treatment of the membrane other than by polymerisation thermal other than drying, e.g. sintering
    • 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 an electrolyte membrane, and relates to a composite electrolyte membrane for a fuel cell having an excellent impregnation property and improved mechanical properties, a membrane-electrode assembly including the same, a fuel cell including the same, and a manufacturing method thereof.
  • a fuel cell is a power generation system that directly converts chemical energy generated by electrochemical reaction between fuel (hydrogen or methanol) and oxidant (oxygen) to electrical energy.It is an eco-friendly feature with high energy efficiency and low emission of pollutants. Research and development.
  • the fuel cell can be used by selecting a fuel cell for high temperature and low temperature according to the application field, and is generally classified according to the type of electrolyte. For high temperature, a solid oxide fuel cell (SOFC) and molten carbonate are used.
  • SOFC solid oxide fuel cell
  • MCFC molten carbonate
  • Fuel cell Molten Carbonate Fuel Cell, MCFC
  • AFC Alkaline Fuel Cell
  • PEMFC Polymer Electrolyte Membrane Fuel Cell
  • PEMFC hydrogen ion exchange membrane fuel cell
  • DMFC Direct Methanol Fuel Cell
  • the unit cell structure of the fuel cell has a structure in which an anode (anode, fuel electrode) and a cathode (cathode, oxygen electrode) are coated on both sides of an electrolyte membrane made of a polymer material, which is a membrane-electrode assembly (Membrane). Electrode Assembly (MEA).
  • the membrane-electrode assembly (MEA) is a portion in which an electrochemical reaction between hydrogen and oxygen occurs and is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane (eg, a hydrogen ion conductive electrolyte membrane).
  • hydrogen or methanol which is a fuel, is supplied to generate an oxidation reaction of hydrogen to generate hydrogen ions and electrons.
  • water is generated by a reduction reaction of oxygen by combining hydrogen ions and oxygen that have passed through the polymer electrolyte membrane. .
  • This membrane-electrode assembly has a form in which the electrode catalyst layers of the anode and the cathode are coated on both sides of the ion conductive electrolyte membrane.
  • Membrane-electrode assembly (MEA), which can be seen as a key component of the electrochemical reaction of fuel cells, is especially used for ion-conducting electrolyte membranes and platinum catalysts, which have a high price ratio, and is directly related to power production efficiency. It is considered as the most important part in improving the performance and increasing the price competitiveness.
  • Conventional methods for preparing MEAs that are commonly used include preparing a paste by mixing a catalyst material, a hydrogen ion conductive binder, ie, a fluorine-based Nafion ionomer, and water and / or an alcohol solvent, It is coated with a carbon cloth or carbon paper that serves as an electrode support that supports the catalyst layer and at the same time serves as a gas diffusion layer, and then dry and heat-bond the hydrogen ion conductive electrolyte membrane.
  • Redox reaction of hydrogen and oxygen by the catalyst in the catalyst layer Transfer of electrons by tightly bonded carbon particles; Securing passages for supplying hydrogen, oxygen and moisture and for discharging excess gas after the reaction;
  • the movement of oxidized hydrogen ions must be carried out at the same time.
  • the area of the triple phase boundary where the feed fuel, the catalyst and the ion conductive polymer electrolyte membrane meet must be increased to reduce the activation polarization, and the interface between the catalyst layer and the electrolyte membrane and the catalyst layer The interface between the gas diffusion layer and the gas must be uniformly bonded to reduce ohmic polarization at the interface.
  • the MEA having the above-described structure typically uses a thick electrolyte membrane, the transfer of hydrogen ions may be delayed, thereby degrading performance.
  • the present invention has been made to solve the above problems, a composite electrolyte membrane for a fuel cell having an excellent impregnation and improved mechanical properties, a membrane-electrode assembly comprising the same, a fuel cell comprising the same, and a method of manufacturing the same
  • the purpose is to provide.
  • Another object of the present invention is to provide a composite electrolyte membrane for a fuel cell, a membrane-electrode assembly including the same, and a method for manufacturing a fuel cell including the same, which can simplify the manufacturing process.
  • the present invention includes a fluorine-based ionomer in the surface and pores of the PTFE porous support and the PTFE porous support, the pores formed in the PTFE porous support is 10 to 50%, the average diameter of less than 100 nm of the average diameter It provides a composite electrolyte membrane for a fuel cell, characterized in that it comprises 20 to 60% of the pore of 100 ⁇ 500 nm and -10 to 50% of the pore exceeding the average diameter of 500 nm.
  • the fuel cell composite electrolyte membrane may have a volume of at least 90% by volume of the pores occluded with respect to the volume of the entire pore.
  • the fluorine-based ionomer may include one or more selected from the group consisting of Nafion, Flemion, and Aciplex.
  • the surface and pores of the PTFE porous support may further include at least one moisture absorbent selected from zeolite, titania, zirconia, and montmorillonite.
  • the platinum-carrying carbon particles may be included in the surface and pores of the PTFE porous support, the platinum-carrying carbon particles are the first carbon particles and the average diameter of 1 ⁇ 3 ⁇ m average diameter
  • the second carbon particles of 300 nm or less may be included alone or in combination.
  • the diameter distribution ratio may satisfy the following Equation 1.
  • D 50 and D 90 each represent a lower 50% and a 90% diameter distribution of the carbon particles.
  • the platinum-carrying carbon particles may include the first carbon particles and the second carbon particles in a weight ratio of 1: 0.1-5.
  • a composite electrolyte for a fuel cell comprising forming a PTFE porous support comprising pores having a predetermined aspect ratio, impregnating the PTFE porous support in a fluorine ionomer solution and drying and heat-treating the impregnated PTFE porous support
  • a composite electrolyte for a fuel cell comprising forming a PTFE porous support comprising pores having a predetermined aspect ratio, impregnating the PTFE porous support in a fluorine ionomer solution and drying and heat-treating the impregnated PTFE porous support
  • the surface of the PTFE porous support and may include platinum-carrying carbon particles in the pores, the platinum-carrying carbon particles are the first carbon particles having an average diameter of 1 ⁇ 3 ⁇ m and the average diameter 300
  • the second carbon particles of nm or less may be included alone or in combination.
  • the diameter distribution ratio may satisfy the following Equation 1.
  • D 50 and D 90 each represent a lower 50% and a 90% diameter distribution of the carbon particles.
  • the platinum-carrying carbon particles may include the first carbon particles and the second carbon particles in a weight ratio of 1: 0.1-5.
  • the PTFE porous support may be formed by sintering a biaxially stretched PTFE sheet, the biaxial stretching may be 1: 1 to 5 to 15 biaxial stretching ratio and biaxial stretching ratio have.
  • the sintering may be performed at a temperature of 250 °C ⁇ 450 °C.
  • the biaxially stretched PTFE sheet forming a paste containing 10 to 20 parts by weight of lubricant with respect to 100 parts by weight of PTFE fine powder having a specific gravity of 2.14 to 2.17, the paste Aging for 10 to 15 hours at a temperature of 50 to 90 °C, compressing the aged paste to produce a PTFE block, extruding the PTFE block at 400 ⁇ 800 psi pressure to form a PTFE sheet,
  • the PTFE sheet may be dried to remove the lubricant and biaxially stretch the PTFE sheet from which the lubricant is removed.
  • the PTFE porous support may have an average pore size of 0.10 ⁇ 0.50 ⁇ m, porosity may be 60 ⁇ 90%.
  • the fluorine ionomer solution may comprise 75 to 95% by weight of the solvent and 5 to 25% by weight of the fluorine ionomer.
  • the fluorine-based ionomer may include one or more selected from Nafion, Flemion, and Aciplex, the fluorine-based ionomer solution It may further comprise one or more moisture absorbents selected from zeolite, titania, zirconia, and montmorillonite.
  • the drying may be performed for 1 minute to 30 minutes at 60 to 100 temperature
  • the heat treatment may be performed for 1 minute to 5 minutes at 100 to 200 temperature.
  • the present invention provides a membrane-electrode assembly, which is bonded to both surfaces of the above-described fuel cell composite electrolyte membrane and the fuel cell composite electrolyte membrane, and includes an electrode including a catalyst layer and a gas diffusion layer. do.
  • the PTFE porous support may be disposed such that the major axis of the pores is directed in the direction of the current flowing between the electrodes.
  • the present invention includes the membrane-electrode assembly and the separator, the electric generator for generating electricity through the electrochemical reaction of the fuel and the oxidant, the fuel for supplying the fuel to the electricity generator It provides a fuel cell including a supply unit and an oxidant supply unit for supplying an oxidant to the generator.
  • the composite electrolyte membrane for a fuel cell according to the present invention, a membrane-electrode assembly including the same, a fuel cell including the same, and a manufacturing method thereof have an effect of excellent impregnation and improved mechanical properties.
  • the manufacturing process can be simplified.
  • FIG. 1 is a schematic diagram of a membrane-electrode assembly according to an embodiment of the present invention.
  • the interface between the catalyst layer and the electrolyte membrane and the interface between the catalyst layer and the gas diffusion layer are generally increased as the movement and use time of hydrogen ions increases during driving of a fuel cell.
  • the adhesion is weakened and separated from each other when applied to the fuel cell, it may cause a decrease in the performance of the fuel cell, and there is a problem in that impregnation and mechanical properties cannot be improved at the same time.
  • the present invention includes a fluorine-based ionomer in the surface and pores of the PTFE porous support and the PTFE porous support, wherein the pores formed in the PTFE porous support have a specific pore distribution to provide a composite electrolyte membrane for a fuel cell.
  • a solution was sought. Through this, it is possible to achieve the effect of improving the mechanical properties while at the same time excellent in impregnation unlike the conventional invention.
  • Such a composite electrolyte membrane for a fuel cell of the present invention will be described as follows.
  • a PTFE porous support comprising pores having a predetermined aspect ratio, impregnating the PTFE porous support with a fluorine ionomer solution, and drying and heat-treating the impregnated PTFE porous support.
  • the PTFE porous support may be formed by sintering a biaxially stretched PTFE sheet, and the biaxially stretched PTFE sheet includes a paste including 10 to 20 parts by weight of a lubricant based on 100 parts by weight of PTFE fine powder having a specific gravity of 2.14 to 2.17.
  • Forming a step the paste is aged at a temperature of 50 to 90 ° C. for 10 to 15 hours, compressing the aged paste to prepare a PTFE block, and extruding the PTFE block at a pressure of 400 to 800 psi.
  • Forming a PTFE sheet, drying the PTFE sheet to remove the lubricant, and biaxially stretched the PTFE sheet from which the lubricant is removed can be prepared.
  • the PTFE fine powder may be a specific gravity 2.14 ⁇ 2.17, preferably may be a specific gravity 2.15 ⁇ 2.16. If the specific gravity of the PTFE fine powder is less than 2.14, the average porosity of the formed PTFE porous membrane is less than 100 nm, so that impregnation of the electrolyte is difficult during the production of a fuel cell composite membrane. If the specific gravity of the PTFE fine powder exceeds 2.17, the average pore size of the PTFE porous membrane formed may exceed 500nm may cause a problem that the mechanical strength is lowered.
  • the mixed solution may include 10 to 20 parts by weight of lubricant, preferably 12 to 18 parts by weight, based on 100 parts by weight of PTFE fine powder. If the lubricant is less than 10 parts by weight, the porosity may be lowered when forming the PTFE porous support by the biaxial stretching process described below. When the lubricant is more than 20 parts by weight, the pore size increases when the PTFE porous support is formed, and thus the strength of the electrolyte membrane becomes weak. Can be.
  • the step of aging the paste may be performed for 10 to 15 hours at a temperature of 50 °C to 90 °C, preferably for 11 to 14 hours at 60 °C to 80 °C. If the aging temperature is less than 50 °C or aged time is less than 10 hours, the elongation of the PTFE sheet may be limited during biaxial stretching, which will be described later, the size of the pores when forming the PTFE porous support is greater than 90 °C or more than 15 hours It may become large and the strength of the electrolyte membrane may be weakened.
  • the step of preparing the PTFE block is not particularly limited as long as it is a process of blocking the PTFE, it can be preferably performed by compressing in a compressor.
  • the forming of the PTFE sheet is not particularly limited as long as it is a method capable of forming the sheet into a PTFE block, and preferably, the PTFE block may be extruded at 400 to 800 psi to form a PTFE sheet. More preferably, the PTFE chip may be extruded at a pressure of 500 to 700 psi to form a PTFE sheet. If the extruding pressure is less than 400 psi, the size of the pores may be increased when the PTFE porous support is formed, and the strength of the electrolyte membrane may be weakened. When the extrusion pressure is greater than 800 psi, the porosity when the PTFE porous support is formed by the biaxial stretching process described below will be described. Can be lowered.
  • the step of removing the lubricant can be used without limitation as long as it is a method of drying the PTFE in general.
  • the dried PTFE sheet is a conventional PTFE sheet is conveyed through the roller, it can be uniaxial stretching by stretching in the longitudinal direction using the speed difference between the rollers, but is not limited thereto.
  • the strain ratio in the longitudinal direction may be 1: 1.1 to 2. If the strain ratio in the longitudinal direction is less than 1: 1.1, the pore size of the PTFE porous support formed by biaxial stretching is small, so that the impregnation amount of the fluorine ionomer described later may be limited. In addition, when the strain ratio in the longitudinal direction exceeds 2, the thickness of the uniaxial stretched sheet may be difficult to give a thickness gradient. In addition, the stretching temperature may be 150 ⁇ 250 °C but is not limited thereto.
  • the uniaxially stretched PTFE sheet is biaxially stretched.
  • the biaxial stretching process is performed at a draw ratio different from the uniaxial stretching.
  • the pores of the biaxially stretched PTFE porous support have a predetermined aspect ratio. Therefore, when the composite electrolyte membrane for a fuel cell according to an embodiment of the present invention is applied to the membrane-electrode assembly, the direction of the major axis of the pores is arranged to be the direction of the transfer of hydrogen ions, that is, the direction of the current, so that the hydrogen ions in the major axis direction The transmission power is improved. Thus, battery characteristics can be improved.
  • Biaxial stretching may be performed in a direction perpendicular to the uniaxial stretching. Like uniaxial stretching, biaxial stretching can also be carried through the rollers and stretched transversely using the speed difference between the rollers.
  • the present invention is not limited thereto and may be stretched according to the stretching method used in manufacturing a conventional sheet. Strain ratio in the transverse direction may be 1: 6 to 30. If the strain ratio in the transverse direction is less than 1: 6, the effect of improving hydrogen ion transfer force may be insignificant as the aspect ratio of the pores of the PTFE porous support becomes smaller. In addition, when the strain ratio in the transverse direction exceeds 30, the fibril and node structures of the transversely stretched sheet may be destroyed.
  • the biaxial stretching may be carried out at 200 °C to 320 °C, preferably 280 °C to 320 °C the PTFE sheet. If the biaxial stretching temperature is less than 200 ° C., the pore size of the PTFE porous membrane may be reduced in the stretching process, and if the temperature exceeds 320 ° C., the pore size of the PTFE porous membrane may be increased.
  • the biaxial stretching may be a uniaxial stretching ratio and a biaxial stretching ratio of 1: 5 to 15, preferably 1: 7 to 13. If the uniaxial draw ratio and the biaxial draw ratio are less than 1: 5, the pore size of the PTFE porous membrane may be reduced, so that the ionomer impregnation may be difficult, and the monoaxial draw ratio and the biaxial draw ratio exceed 1:15, so that the production The problem may be that the mechanical strength of one PTFE porous membrane is reduced.
  • the sintering may be formed by sintering the biaxially stretched PTFE sheet at a temperature of 250 °C to 450 °C, preferably at a temperature of 300 °C to 400 °C to form a PTFE porous support. If the sintering temperature is less than 250 °C the strength of the PTFE porous support may be lowered, if it exceeds 400 °C may be inferior sintering effect due to the temperature rise.
  • the PTFE porous support formed through the sintering may have an average pore size of 0.10 to 0.50 ⁇ m, a porosity of 60 to 90%, and preferably an average pore size of 0.20 to 0.40 ⁇ m and a porosity of 80 to 85%. Can be. If the average pore size is less than 0.10 ⁇ m or the porosity is less than 60%, the degree of impregnation of the fluorine-based ionomer solution into the pores may be limited. In addition, when the average pore size exceeds 0.50 ⁇ m or the porosity exceeds 90%, the PTFE porous support structure may be modified when impregnated with the fluorine ionomer solution in the impregnation process described later.
  • the fluorine-based ionomer solution is filled in the pores of the PTFE porous support.
  • the fluorine ionomer solution may further include at least one hygroscopic agent selected from the group consisting of zeolite, titania, zirconia and montmorillonite.
  • the moisture absorbent is further included, the amount of fluorine-based ionomer solution impregnation on the PTFE porous support may be further increased.
  • the fluorine-based ionomer may include one or more selected from the group consisting of Nafion, Flemion, and Aciplex, and more preferably Nafion.
  • the fluorine ionomer solution may include 75 to 95 wt% of a solvent and 5 to 25 wt% of a fluorine ionomer, preferably 80 to 90 wt% of a solvent and 10 to 20 wt% of a fluorine ionomer.
  • the solvent is not limited as long as it is usually used as a solvent of the fluorine ionomer, preferably distilled water, n-propanol, isopropanol, Ethanol, NMP, DMAc, or the like.
  • the fluorine-based ionomer solution may include 0.05 to 5 parts by weight of platinum-carrying carbon particles based on 100 parts by weight of the fluorine-based ionomer solution. If the platinum-carrying carbon particles are less than 0.05 parts by weight with respect to 100 parts by weight of the fluorine-based ionomer solution, a problem of insufficient effect of the additive may occur. If the amount is more than 5 parts by weight, the ionomer content in the solid content is small, thereby reducing the ion conductivity. May occur.
  • the diameter distribution ratio may satisfy the following Equation 1.
  • D 50 and D 90 each represent a lower 50% and a 90% diameter distribution of the carbon particles.
  • Equation 1 If the ratio of D 50 and D 90 according to Equation 1 is less than 1.2, it may be difficult to produce uniform carbon particles, which may cause a problem of increasing prices. Ionomer impregnation may occur due to scleral pore closure.
  • the first carbon particles and the second carbon particles when including the first carbon particles and the second carbon particles in a mixture, the first carbon particles and the second carbon particles in a weight ratio of 1: 0.1 to 5, preferably in a weight ratio of 1: 0.2 to 2 It may include.
  • the liquid retention property of the impregnated fluorine-based ionomer solution may be improved, and the adhesion to the electrode may be improved when the membrane-electrode assembly is manufactured.
  • the drying may be carried out for 1 to 30 minutes at a temperature of 60 to 100 °C, preferably for 5 to 20 minutes at 65 to 95, the heat treatment for 1 to 5 minutes at a temperature of 100 to 200, preferably At 120-180 for 2-4 minutes. If the drying temperature is less than 60 or less than 1 minute, a problem may occur that the liquid retention of the fluorine-based ionomer solution impregnated in the PTFE porous support may be reduced. In manufacturing the electrode assembly, adhesion with the electrode may be reduced. In addition, if the heat treatment temperature is less than 100 or less than 1 minute, a problem may occur that the liquid retention property of the fluorine-based ionomer solution impregnated in the PTFE porous support may be reduced. When manufacturing the electrode assembly, a problem may occur in that adhesiveness with the electrode is lowered.
  • the volume of the pores occluded in the heat treated PTFE porous support may be at least 90% by volume, preferably at least 93% by volume relative to the total pore volume.
  • the composite electrolyte membrane for a fuel cell according to the present invention prepared by the manufacturing method includes a fluorine-based ionomer in the surface and pores of the PTFE porous support and the PTFE porous support, the pores formed in the PTFE porous support has an average diameter of less than 100 nm 10 to 50% of pores, 20 to 60% of pores with an average diameter of 100 to 500 nm and 10 to 50% of pores exceeding an average diameter of 500 nm, preferably 20 to 40% of pores with an average diameter of less than 100 nm and an average diameter It may include 30 to 50% of the pore of 100 to 500 nm and 20 to 40% of the pore exceeding the average diameter of 500 nm.
  • the pore less than the average diameter of 100 nm is less than 10% may cause a problem of poor mechanical properties, if more than 50% may cause a problem of poor impregnation.
  • the average pore size of 100 to 500 nm is less than 20%, a problem may occur as long as the uniformity of the PTFE porous membrane is reduced, and if it exceeds 60%, problems of impregnation and mechanical strength may not be improved at the same time. Can be.
  • the pore exceeding the average diameter of 500 nm is less than 10% may cause a problem of poor impregnation, if more than 50% may cause a problem of poor mechanical properties.
  • the composite electrolyte membrane for a fuel cell according to the present invention has the effect of improving the impregnation and mechanical properties. Specifically, the impregnability is improved so that the thickness variation coefficient (CV1) value according to the following relation 2 is 13% or less, preferably 12% or less, the weight variation coefficient (CV2) value according to the relation 3 is 170% or more, Preferably at least 200%.
  • CV1 thickness variation coefficient
  • CV2 weight variation coefficient
  • Thickness variation coefficient (CV1,%) ((Composite electrolyte membrane thickness for fuel cell-PTFE porous support thickness) / (PTFE porous support thickness)) ⁇ 100
  • Weight variation coefficient (CV2,%) ((Full weight of composite electrolyte membrane for fuel cell-PTFE porous support weight) / (PTFE porous support weight)) ⁇ 100
  • the composite electrolyte membrane for a fuel cell according to the present invention may have a tensile strength of 28 to 60 MPa, preferably a tensile strength of 29 to 59 MPa.
  • the method of manufacturing a membrane-electrode assembly includes the steps of preparing the above-described fuel cell composite electrolyte membrane, and bonding the electrode including a catalyst layer and a gas diffusion layer to both surfaces of the fuel cell composite electrolyte membrane. It includes.
  • FIG. 1 is a schematic diagram of a membrane-electrode assembly according to an embodiment of the present invention.
  • the membrane-electrode assembly includes an oxide electrode 20 and a reduction electrode 20 ′ positioned to face each other with a composite electrolyte membrane 10 for a fuel cell interposed therebetween.
  • the oxidation electrode 20 and the reduction electrode 20 ' include gas diffusion layers 21 and 21', catalyst layers 22 and 22 ', and electrode substrates 23 and 23', respectively.
  • the anode 20 may include a gas diffusion layer 21 and an oxidation catalyst layer 22.
  • the gas diffusion layer 21 may be provided to prevent rapid diffusion of fuel injected into the fuel cell and to prevent a decrease in ion conductivity.
  • the gas diffusion layer 21 may control the diffusion rate of the fuel through heat treatment or electrochemical treatment.
  • the gas diffusion layer 21 may be carbon fiber or carbon paper.
  • the fuel may be a liquid fuel such as formic acid solution, methanol, formaldehyde, or ethanol.
  • the oxidation catalyst layer 22 is a layer into which the catalyst is introduced, and may include a conductive support and an ion conductive binder (not shown).
  • the oxidation catalyst layer 22 may include a main catalyst attached to the conductive support.
  • the conductive support may be carbon black and the ion conductive binder may be a Nafion ionomer or a sulfonated polymer.
  • the main catalyst may be a metal catalyst, for example, may be platinum (Pt).
  • the oxidation catalyst layer 22 may be formed using an electroplating method, a spray method, a painting method, a doctor blade method, or a transfer method.
  • the reduction electrode 20 ′ may include a gas diffusion layer 21 ′ and a reduction catalyst layer 22 ′.
  • the gas diffusion layer 21 ′ may be provided to prevent sudden diffusion of the gas injected into the reduction electrode 20 ′ and to uniformly disperse the gas injected into the reduction electrode 20 ′.
  • the gas diffusion layer 21 may be carbon paper or carbon fiber.
  • the reduction catalyst layer 22 ′ is a layer into which the catalyst is introduced, and may include a conductive support and an ion conductive binder (not shown).
  • the reduction catalyst layer 22 ′ may include a main catalyst attached to the conductive support.
  • the conductive support may be carbon black and the ion conductive binder may be a Nafion ionomer or a sulfonated polymer.
  • the main catalyst may be a metal catalyst, for example, may be platinum (Pt).
  • the reduction catalyst layer 22 ′ may be formed using an electroplating method, a spray method, a painting method, a doctor blade method, or a transfer method.
  • the membrane-electrode assembly may be formed by placing and then fastening each of the anode electrode 20, the composite electrolyte membrane for fuel cell 10, and the cathode 20 ′, or may be formed by pressing them at high temperature and high pressure.
  • Bonding the electrodes 20 and 20 'to both surfaces of the composite electrolyte membrane 10 for a fuel cell may first apply a gas diffusion layer forming material to one surface of the composite electrolyte membrane 10 for a fuel cell, thereby forming a gas diffusion layer 21. 21 ').
  • the gas diffusion layers 21 and 21 ′ serve as current conductors between the composite electrolyte membrane 10 for fuel cells and the catalyst layers 22 and 22 ′, and serve as passages of reactant gases and water as products. Therefore, the gas diffusion layers 21 and 21 ′ may have a porous structure having a porosity of 20 to 90% to allow gas to pass therethrough.
  • the thicknesses of the gas diffusion layers 21 and 21 ' may be appropriately adopted as necessary, and may be, for example, 100 to 400 ⁇ m. When the thickness of the gas diffusion layers 21 and 21 'is 100 ⁇ m or less, the electrical contact resistance increases between the catalyst layer and the electrode substrate, and the structure may become unstable by compression. In addition, when the thickness of the gas diffusion layers 21 and 21 ′ exceeds 400 ⁇ m, it may be difficult to move the reactant gas.
  • the gas diffusion layers 21 and 21 ′ may be formed of a carbonaceous material and a fluorine resin.
  • Carbonaceous materials include graphite, carbon black, acetylene black, denka black, kecheon black, activated carbon, mesoporous carbon, carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon nanorings, carbon nanowires, and fullerenes (C60).
  • super P may include one or more selected from the group consisting of, but is not limited thereto.
  • the copolymer of polytetrafluoroethylene, polyvinylidene fluoride (PVdF), polyvinyl alcohol, cellulose acetate, polyvinylidene fluoride-hexafluoropropylene, or styrene-butadiene high part (SBR) may include one or more selected from the group consisting of.
  • catalyst layers 22 and 22 ' are formed on the gas diffusion layers 21 and 21'.
  • the catalyst layers 22 and 22 ' may be formed by applying a catalyst layer forming material on the gas diffusion layers 21 and 21'.
  • the catalyst layer forming material may be a metal catalyst or a metal catalyst supported on a carbon-based support.
  • the metal catalyst at least one selected from the group consisting of platinum, ruthenium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, and platinum-transition metal alloy may be used.
  • the carbon-based support graphite (graphite), carbon black, acetylene black, denka black, kecheon black, activated carbon, mesoporous carbon, carbon nanotubes, carbon nanofibers, carbon nanohorn, carbon nano ring, carbon nano And at least one selected from the group consisting of wire, fullerene, and superP.
  • the electrode substrates 23 and 23 ' may be a conductive substrate selected from the group consisting of carbon paper, carbon cloth, and carbon felt, but are not limited thereto, and may be a cathode electrode material or an anode electrode material applicable to a polymer electrolyte fuel cell. Are all available.
  • the electrode substrate may be formed through a conventional deposition method, and after forming the catalyst layers 22 and 22 'on the electrode substrates 23 and 23', the catalyst layers on the gas diffusion layers 21 and 21 'are formed. 22 and 22 'and the gas diffusion layers 21 and 21' may be disposed to be in contact with each other.
  • the fuel cell according to an embodiment of the present invention is at least one electricity generating unit for generating electrical energy through the oxidation reaction of the fuel and the reduction reaction of the oxidant, and the fuel for supplying the above-described fuel to the electricity generating unit It comprises a supply part and an oxidant space
  • the membrane-electrode assembly may include one or more, and separators for supplying fuel and an oxidant are disposed at both ends of the membrane-electrode assembly to constitute an electricity generator. At least one of the electricity generating units may be combined to form a stack.
  • the arrangement or manufacturing method of the fuel cell can be formed without limitation as long as it is applicable to the polymer electrolyte fuel cell, it can be variously applied with reference to the prior art.
  • liquid lubricant 15 parts by weight of the liquid lubricant was mixed and blended with respect to 100 parts by weight of the PTFE fine powder having a specific gravity of 2.15, and aged at 70 ° C. for 12 hours to prepare a PTFE block using a molding jig. Thereafter, the PTFE block was put in an extrusion mold and subjected to pressure extrusion under 600 psi pressure. The sheet was rolled to a thickness of 0.3 mm through a rolling roll, and then a lubricant was removed through a drying process to prepare a PTFE sheet.
  • the PTFE porous support prepared by the above method had a maximum pore size of 0.83 ⁇ m, an average pore size of 0.35 ⁇ m, and a porosity of 75%.
  • the PTFE porous support was fixed on the PET film, and 20% by weight of Nafion which is a fluorine ionomer was used as a fluorine ionomer solution.
  • the fluorine ionomer solution was mixed with 0.5 parts by weight of platinum-carrying carbon particles based on 100 parts by weight of the fluorine ionomer solution.
  • a fluorine-based ionomer solution was applied, dried in a vacuum oven at a temperature of 80 ° C. for 10 minutes, and heat treated for 3 minutes at a temperature of 160 ° C. to prepare a composite electrolyte membrane for a fuel cell having a thickness of 20 ⁇ m.
  • the platinum-carrying carbon particles include first carbon particles having an average diameter of 2 ⁇ m and second carbon particles having an average diameter of 150 nm at a weight ratio of 1: 1.5, and each of the first carbon particles and the second carbon particles has an average weight. 20 wt% of platinum having a diameter of 3 nm, and the first carbon particles had a ratio of D 50 and D 90 according to the following relational formula 1 to 1.5.
  • D 50 and D 90 each represent a diameter distribution of the lower 50% and the 90% of the carbon particles.
  • Preparation was carried out in the same manner as in Example 1, but by varying the draw ratio, draw temperature, fine powder density and carbon particle content as shown in Table 1 and Table 2 to prepare a composite electrolyte membrane for a fuel cell.
  • Longitudinal stretch ratio The axial stretch ratio was 1: except that biaxial stretching was carried out in the same manner as in Example 1 to prepare a composite electrolyte membrane for a fuel cell.
  • Longitudinal stretch ratio The axial stretch ratio was carried out under the same conditions as in Example 1 except biaxial stretching at a ratio of 1:18 to prepare a composite electrolyte membrane for a fuel cell.
  • a composite electrolyte membrane for a fuel cell was prepared under the same conditions as in Example 1 except that the stretching temperature was biaxially stretched at 180 ° C.
  • a composite electrolyte membrane for a fuel cell was prepared under the same conditions as in Example 1 except that the stretching temperature was biaxially stretched to 340 ° C.
  • the thicknesses were measured at arbitrary ten points, and the average value of the thicknesses for the ten points was calculated. It was calculated through the following relation 2 to apply the thickness value in the thickness variation coefficient. This is shown in Table 1 and Table 2 below.
  • Thickness variation coefficient (CV1,%) ((Composite electrolyte membrane thickness for fuel cell-PTFE porous support thickness) / (PTFE porous support thickness)) ⁇ 100
  • Weight variation coefficient (CV2,%) ((Full weight of composite electrolyte membrane for fuel cell-PTFE porous support weight) / (PTFE porous support weight)) ⁇ 100
  • the sample was cut into a size of 10 mm x 50 mm according to ASTM-D882, and then, in a UTM (Universal esting Machine) Tensile strength was measured while pulling at 50 mm / min. The tensile strength is shown in Tables 1 and 2 below.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Example 8 Elongation ratio 1:10 1: 6 1:14 1:10 1:10 1:10 1:10 1:10 Biaxial stretching Drawing temperature (°C) 280 280 280 220 330 280 280 280 PTFE fine powder specific gravity 2.15 2.15 2.15 2.15 2.13 2.145 2.165 Platinum supported carbon particle content (part by weight) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Less than 100nm in diameter (%) 22 45 22 37 15 39 32 18 100 ⁇ 500nm diameter (%) 50 30 32 45 51 32 43 45 Over 500nm diameter (%) 28 15 47 18 34 29 25 27 Thickness variation coefficient (%) 8 8 9 8 9 9 9 8 Weight variation coefficient (%) 224 171 211 181 211 165 178 206 Tensile Strength (MPa) 57 51 28 50 29 31 45 28
  • Examples 1 to 5, 7, 8, and 11, which satisfy specific pore ratios, are omitted from any one of Examples 6, 9, and 10.
  • the thickness variation coefficient was low, the weight variation coefficient was high, and the tensile strength was excellent.

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Abstract

La présente invention concerne une membrane électrolytique, et plus spécifiquement, une membrane électrolytique composite pour une pile à combustible, un ensemble membrane-électrodes comprenant une telle membrane, une pile à combustible comprenant un tel ensemble, et un procédé de fabrication d'une membrane électrolytique composite pour une pile à combustible, d'un ensemble membrane-électrodes comprenant une telle membrane, et d'une pile à combustible comprenant un tel ensemble, la membrane électrolytique composite pour une pile à combustible possédant les effets d'avoir d'excellentes propriétés d'imprégnation ainsi que des propriétés physiques mécaniques améliorées.
PCT/KR2016/003556 2016-04-05 2016-04-06 Membrane électrolytique composite pour pile à combustible, ensemble membrane-électrodes comportant une telle membrane, pile à combustible comportant un tel ensemble, et procédé pour la fabrication de membrane électrolytique composite pour pile à combustible, d'ensemble membrane-électrodes comportant une telle membrane, de pile à combustible comportant un tel ensemble WO2017175892A1 (fr)

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KR102008400B1 (ko) * 2018-02-14 2019-08-08 코오롱머티리얼 주식회사 고분자 전해질 막
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KR20230070598A (ko) 2021-11-15 2023-05-23 코오롱인더스트리 주식회사 고분자 전해질막, 이의 제조 방법 및 이를 포함하는 막-전극 어셈블리

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