WO2016117915A1 - Membrane à électrolyte polymère et son procédé de fabrication - Google Patents

Membrane à électrolyte polymère et son procédé de fabrication Download PDF

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WO2016117915A1
WO2016117915A1 PCT/KR2016/000566 KR2016000566W WO2016117915A1 WO 2016117915 A1 WO2016117915 A1 WO 2016117915A1 KR 2016000566 W KR2016000566 W KR 2016000566W WO 2016117915 A1 WO2016117915 A1 WO 2016117915A1
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polymer electrolyte
electrolyte membrane
membrane
hierarchical structure
fuel cell
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PCT/KR2016/000566
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English (en)
Korean (ko)
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최만수
성영은
조혜성
강윤식
김상문
장세근
김민형
Original Assignee
재단법인 멀티스케일 에너지시스템 연구단
서울대학교산학협력단
기초과학연구원
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Publication of WO2016117915A1 publication Critical patent/WO2016117915A1/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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • 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]
    • H01M8/1006—Corrugated, curved or wave-shaped 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
    • H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1055—Inorganic layers on the polymer electrolytes, e.g. inorganic coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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 polymer electrolyte membrane having a hierarchical microstructure having a fine pattern, and having an increased ion conductivity and effective surface area, a method for manufacturing the same, and an electrochemical energy device using the same.
  • Polymer electrolytes can be broadly classified into two types. The first is a polymer electrolyte in which ions of dissociated salts can move in the polymer by adding an electrolytic salt to a polymer containing hetero elements such as oxygen (O), nitrogen (N), and sulfur (S). Electrolytes are applied to lithium and solar cells. Another polymer electrolyte contains fixed ions charged with cations or anions such as sulfonic acid (SO 3 H), phosphoric acid (PO 4 H 2 ), carboxyl group (COOH), ammonium group (NH 4 + ) in the polymer chain. As a polymer material (polyelectrolyte), it is applied to fuel cells and the like.
  • SO 3 H sulfonic acid
  • PO 4 H 2 phosphoric acid
  • COOH carboxyl group
  • NH 4 + ammonium group
  • PEMFC polymer electrolyte membrane fuel cell
  • the basic structure of the polymer electrolyte fuel cell includes an anode (cathode) and a cathode (cathode) composed of a platinum catalyst layer at both ends of the polymer electrolyte membrane, and is made of porous carbon at the outside of the anode and the cathode, respectively.
  • Gas diffusion layer is positioned to form a membrane-electrode-gas diffusion layer assembly.
  • On both sides of the membrane-electrode-gas diffusion layer assembly there is a separation plate which supports the combination and forms a gas passage. Between the separation plate and the gas diffusion layer where the anode is located, hydrogen, fuel, and the separation plate and the cathode are located.
  • the polymer electrolyte membrane used in the polymer electrolyte fuel cell has a hydrogen ion conductivity, and serves to move the hydrogen ions generated from the anode (anode) to the cathode (cathode).
  • the performance of the polymer electrolyte membrane as an ion conductive medium greatly affects the performance of the fuel cell.
  • As a method for improving the performance of the polymer electrolyte membrane there are the following methods.
  • the equivalent weight of the polymer membrane itself is increased to increase the density of the ion conductive active point, or second, the reaction per unit volume of the electrolyte membrane is increased by increasing the reaction area between the catalyst, the reaction gas, and the polymer electrolyte membrane interface.
  • the reaction per unit volume of the electrolyte membrane is increased by increasing the reaction area between the catalyst, the reaction gas, and the polymer electrolyte membrane interface.
  • Various surface modification methods are used to reduce the interfacial resistance between the electrolyte and the catalyst layer or to widen the reaction area of the electrolyte membrane. These methods include a method of forming irregularities by compressing a material having a rough surface on the electrolyte membrane. For example, the surface of the membrane is eroded to form irregularities on the surface of the membrane, and the method of irradiating ions to the surface of the membrane.
  • the method of irradiating ions to the surface of the film is plasma, corona, arc discharge, electron beam, 10s-100s keV ion beam (Polym. Eng. Sci. 27 (11), 861 (1987); Polymer 21, 895 (1980); Polymer 18, 675 (1977); Polym. Eng. Sci. 19, 1373 (1982)).
  • An object of the present invention is to provide a polymer electrolyte membrane having a hierarchical microstructure and a method of manufacturing the same.
  • Another object of the present invention is to provide an energy cell device using the polymer electrolyte membrane, and more specifically, a polymer electrolyte fuel cell.
  • a polymer electrolyte membrane having a hierarchical structure of two or more layers is provided.
  • the polymer electrolyte membrane is integrally formed with a hierarchical structure of two or more layers, and a polymer electrolyte membrane is provided in which one or more layers have the same or different microstereoscopic patterns.
  • the polymer electrolyte membrane has a hierarchical structure of two or more layers, and each layer may have each other or a different fine pattern is formed in an intaglio.
  • the specific surface area of the polymer electrolyte membrane may be 1.9 times or more than that of the polymer electrolyte membrane without the microstereoscopic pattern.
  • the thickness of the thickest portion of the polymer electrolyte membrane may be 50 ⁇ m or less, and may have a hierarchical microstructure having a thickness of 10 ⁇ m or more.
  • a method of manufacturing a polymer electrolyte membrane having a hierarchical structure comprising a.
  • the hierarchical structure may be a microstereoscopic pattern is formed in one or more of the two or more layers.
  • the hierarchical microstructure may be one in which the two or more layers are all formed with each other, or different fine three-dimensional patterns are embossed.
  • the temperature of step c) may be heat-compressed at a temperature below the glass transition temperature (T g ) of the polymer electrolyte membrane material and at a pressure of 10 to 20 kg / cm -2 .
  • an energy cell device using the polymer electrolyte membrane.
  • the polymer electrolyte fuel cell may use a membrane electrode assembly in which a catalyst layer is formed as an electrode on both sides of the polymer electrolyte membrane.
  • the polymer electrolyte fuel cell may further include a gas diffusion layer on both sides of the membrane electrode assembly.
  • the electrochemically active area of the membrane electrode assembly may be 65 m 2 / g or more.
  • the maximum power density of the polymer electrolyte fuel cell has a H 2 / O 2 stoichiometric ratio of 2.0 / 9.5, the polymer electrolyte does not have a hierarchical structure having the fine pattern at a condition of 1 atm of 80 °C. 40% than with membrane It may be higher than that.
  • the maximum power density of the polymer electrolyte fuel cell has a stoichiometric ratio of H 2 / O 2 of 2.0 / 9.5, using a polymer electrolyte membrane having no hierarchical structure having the micropattern at 150 kPa. It may be 9% higher than that.
  • the resistance due to ion migration of the polymer electrolyte membrane may be reduced by 15% or more than the resistance of the polymer electrolyte membrane having no hierarchical structure having the micropattern.
  • the average membrane thickness may be reduced to reduce its ion conductivity and resistance characteristics, and the problem of deterioration of mechanical properties due to the reduction of the membrane thickness may also be solved.
  • the catalyst layer is directly coated on the polymer electrolyte membrane whose surface area is increased by the hierarchical structure, thereby reducing the contact resistance between the catalyst layer and the electrolyte membrane.
  • the hydrogen ion transfer resistance is reduced, so that the performance of the battery can be improved even with a small amount of catalyst.
  • FIG. 1 is a cross-sectional view of a hierarchical microstructured polymer electrolyte membrane according to one embodiment.
  • FIG. 2 is a schematic diagram of a method of manufacturing a hierarchical microstructured polymer electrolyte membrane according to one embodiment.
  • SEM scanning electron microscope
  • Figure 4 compares the specific surface area of the polymer electrolyte membrane according to Example 1 and Comparative Examples 1 to 4.
  • FIG. 5 is a graph comparing power densities of unit cells prepared from the polymer electrolyte membranes of Example 1 and Comparative Examples 1 to 4.
  • FIG. 5 is a graph comparing power densities of unit cells prepared from the polymer electrolyte membranes of Example 1 and Comparative Examples 1 to 4.
  • Example 6 is a CV (Cyclic Voltammogram) graph for measuring the electrochemically active area of the membrane electrode assembly prepared from the polymer electrolyte membrane of Example 1 and Comparative Example 1.
  • Example 7 is a graph measuring the impedance of a unit cell prepared from the polymer electrolyte membrane of Example 1 and Comparative Example 1.
  • the polymer electrolyte membrane according to the present invention is characterized by forming a hierarchical structure of two or more layers.
  • FIG. 1 is a cross-sectional view of a hierarchical microstructured polymer electrolyte membrane according to one embodiment.
  • the polymer electrolyte membrane has a hierarchical structure of two or more layers, and each layer has each other or different fine patterns are intaglio.
  • the size (diameter) of the fine pattern may be selected in the range of 50 nm to 900 ⁇ m.
  • FIG. 1 illustrates that the fine patterns are engraved on all layers, the fine patterns are not formed at all on each layer, or the fine patterns may be engraved on only one layer thereof.
  • the polymer electrolyte membrane having the structure as described above may have a specific surface area increased by 1.9 times or more compared to the polymer electrolyte membrane having the flat structure.
  • the thickness L1 of the thickest part of the polymer electrolyte membrane may be 50 ⁇ m or less, and the thickness L3 of the thinnest part may be 10 ⁇ m or more, between the thinnest part and the thickest part.
  • the thickness (L2) of the layer formed on the may have a value between 10 to 50 ⁇ m.
  • the polymer electrolyte membrane having the hierarchical microstructure as described above may not only reduce ion transfer resistance due to the decrease in thickness, but also improve the decrease in mechanical strength due to the decrease in thickness from the structural characteristics of the hierarchical structure.
  • the microstructure formed in each layer induces a markedly increased specific surface area of the polymer electrolyte, thereby increasing the contact area between the ions and the electrolyte membrane, thereby reducing the ion migration resistance.
  • the polymer electrolyte membrane may be manufactured by a manufacturing method comprising a.
  • a silicon substrate, a metal substrate, a polymer substrate, a glass substrate, a PET film, or the like may be used as the substrate, and it may be preferable that a thermoplastic polymer is used as the polymer substrate.
  • a polymer used as the polymer electrolyte membrane can be used without limitation, for example, polyethylene oxide (PEO), polypropylene oxide (PPO), polyethyleneimine (PEI) ), Polyethylenesulfide (PES), polyvinylacetate (PVAc), polyethylenesuccinate (PESc), polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), poly Vinyl chloride (PVC), polyether ketone (PEK), polybenzimidazole (PBI), sulfonated polyimide, sulfonated polyarylether sulfone, sulfonated polyether ether ketone, sulfonated polybenzimidazole, sulfonated poly It may be any one selected from the group consisting of sulfone, sulfonated polystyrene,
  • the hierarchical microstructures may have two or more layers, and each layer may have a different or three-dimensional microscopic pattern formed on the polymer electrolyte membrane to form a pattern symmetrical with the microstereoscopic pattern formed on the structure.
  • the hierarchical microstructures may include, for example, polyurethane acrylate (PUA), polydimethylsiloxane (PDMS), ethylene ethylene (TFE), perfluoroalkyl acrylate (PFA), perfluoropolyether (PFPE), and PTFE.
  • PUA polyurethane acrylate
  • PDMS polydimethylsiloxane
  • TFE ethylene ethylene
  • PFA perfluoroalkyl acrylate
  • PFPE perfluoropolyether
  • PTFE perfluoropolyether
  • Polytetrafluoroethylene may be prepared by mixing a polymer such as a polymer stamp including one or more selected from one or more, or an inorganic material such as silicon oxide
  • the hierarchical microstructure for transferring the hierarchical micropattern to the polymer electrolyte membrane may be prepared using an imprint lithography method using UV curing or a mold prepared by a polymer polymerization method by heating.
  • the mold may have a form having a hierarchical structure of two or more layers manufactured by a method of using a partially cured layer according to oxygen concentration during UV curing. For example, by forming a partially cured layer on the first polymer pattern film and forming a second pattern on the partially cured layer, a mold capable of manufacturing a structure having a hierarchical microstructure can be formed, and the step By repeating the above, a mold having a hierarchical structure of two or more layers can be produced.
  • the hierarchical microstructure according to the present invention may be manufactured by casting and molding a polymer resin composition forming the hierarchical microstructure in the mold.
  • the micropatterns of the hierarchical microstructures manufactured using the mold as described above may be mainly embossed micropatterns, and thus, the polymer electrolyte membrane of the present invention made of the hierarchical microstructures has a negative microsymmetry.
  • the pattern may be formed.
  • the step of heating the step of forming a pattern on the polymer electrolyte membrane by heat-compressing the hierarchical microstructure is less than the glass transition temperature (T g ) of the material used as the polymer electrolyte membrane And 10 to 60 minutes under pressure of 10 to 20 kg / cm ⁇ 2 .
  • T g glass transition temperature
  • the polymer electrolyte membrane made of Nafion may be heated and compressed near 120 ° C., which is lower than 140 ° C. which is the T g temperature of Nafion.
  • the polymer electrolyte membrane having a hierarchical microstructure manufactured by the above method can be applied to an energy cell device requiring ionic conductivity, that is, low resistance to ion migration.
  • the polymer electrolyte may be classified into two types and may be used in an energy cell device.
  • the polymer electrolyte may be used in a polymer containing hetero elements such as oxygen (O), nitrogen (N), and sulfur (S).
  • Ions of salts dissociated by the addition of sea salts are polymer electrolytes that can move in the polymer, and this type of polymer electrolyte has been applied to lithium batteries and solar cells.
  • Another polymer electrolyte contains fixed ions charged with cations or anions such as sulfonic acid (SO 3 H), phosphoric acid (PO 4 H 2 ), carboxyl group (COOH), ammonium group (NH 4 + ) in the polymer chain. It is a polymer material which is applied to fuel cells.
  • the polymer electrolyte according to the present invention can be usefully applied to an ion exchange membrane of a redox flow battery (RFB).
  • RFB redox flow battery
  • the mechanical properties are maintained while having a thinner thickness and at the same time a fine pattern is formed. Since an electrolyte membrane having a high surface area can be produced, the resistance due to ion migration is reduced, which can lead to an improvement in ion conductivity, and thus can be effective in improving battery performance.
  • the polymer electrolyte membrane according to the present invention has a low average thickness and a high specific surface area, and thus can be more effectively applied to a polymer electrolyte fuel cell.
  • the present invention provides a polymer electrolyte fuel cell manufactured using a membrane electrode assembly, which exhibits an effect of increasing adhesion and contact area between the catalyst and the electrolyte membrane by coating the catalyst on the surface of the polymer electrolyte membrane having a hierarchical microstructure. It is about.
  • the present invention can reduce the average thickness of the membrane without having to decrease the physical properties of the membrane by having a hierarchical structure, and compared with the polymer electrolyte membrane having a flat structure, the hierarchical structure and the fine pattern are formed in a complex to increase the surface area. desirable.
  • the polymer electrolyte used in the present invention includes a polyperfluoro sulfonate polymer membrane of a Nafion polymer membrane system, which is generally used as a hydrogen ion conductive polymer electrolyte. It may be necessary to pretreat the surface of the membrane first to prepare the membrane-electrode binder used in the fuel cell using the polymer electrolyte membrane.
  • the pretreatment of the membrane surface is placed in 2 to 5% by weight of hydrogen peroxide water to remove metal contaminants on the polymer electrolyte membrane, and boiled at a temperature of about 80 ° C. for 1 hour, followed by washing in boiling ultrapure water.
  • the polymer electrolyte membrane is placed in a 0.5 M sulfuric acid solution, boiled at a temperature of about 80 ° C. for 1 hour, and then washed with ultrapure water and dried.
  • the catalyst is directly coated on the pretreated polymer electrolyte membrane to increase adhesion and contact area between the catalyst layer and the polymer electrolyte membrane, thereby generating hydrogen ions generated from the catalyst layer, that is, the electrode. It can be easily moved to the membrane to increase the performance of the fuel cell produced using the polymer electrolyte membrane.
  • a platinum-supported catalyst (hereinafter referred to as Pt / C) on a fine powder carbon black carrier or a catalyst supported on a platinum-ruthenium alloy is used.
  • a coating catalyst slurry can be prepared using this.
  • a predetermined amount of platinum or platinum-ruthenium alloy catalyst is added to a solvent, a Nafion ionomer solution is added thereto, and the catalyst slurry is well dispersed by stirring with an ultrasonic stirrer.
  • a predetermined amount of platinum or platinum-ruthenium alloy catalyst is added to a solvent, a Nafion ionomer solution is added thereto, and the catalyst slurry is well dispersed by stirring with an ultrasonic stirrer.
  • the method of manufacturing an electrode of a fuel cell by a direct coating method of directly coating a catalyst on the surface of the polymer electrolyte is performed by coating the catalyst layers on both surfaces of the polymer electrolyte membrane, wherein the catalyst layer is formed on the polymer electrolyte membrane.
  • spray coating screen printing, brushing, tape casting, decal process, and the like may be used.
  • Spray coating can be used.
  • the spray coating method increases the contact area between the catalyst layer and the polymer electrolyte membrane when the catalyst particles adhere to the intaglio portion of the surface of the polymer electrolyte membrane. In this principle, the spray coating method increases the contact between the catalyst particles and the surface of the electrolyte membrane. Spray coating may be the most effective.
  • the contact area between the catalyst layer and the electrolyte membrane increases, the resistance of hydrogen ions formed in the catalyst layer on the anode side of the anode to move to the electrolyte membrane or the hydrogen ions from the electrolyte membrane to the catalyst layer on the cathode side of the cathode decreases.
  • the performance of a fuel cell manufactured by including a polymer electrolyte membrane having an increased surface area may be improved.
  • the content of platinum or platinum-ruthenium alloy in the prepared catalyst slurry may be preferably 10 to 50% by weight based on the total weight of the catalyst to produce a fuel cell having excellent performance.
  • the Nafion ionomer may be used in an amount of 1/2 to 1/5 of the catalyst weight based on the dry weight of the Nafion content in the catalyst slurry.
  • Isopropanol, normal-butyl acetate, etc. may be used as a solvent that may be used to prepare the catalyst slurry.
  • the thickener may be added to increase the viscosity of the catalyst slurry.
  • glycerin, dimethylsulfoxide, or the like may be used as a thickener that may be used in the present invention.
  • the prepared catalyst slurry was coated with a uniform thickness on both surfaces of the polymer electrolyte membrane using an injector using air pressure, and then dried at room temperature for 12 hours.
  • the amount of the catalyst coated on one side of the polymer electrolyte membrane is 0.05 to 0.4 mg Pt / cm 2 based on the amount of platinum per unit electrolyte membrane area. This amount can be very small compared to the amount of catalyst used in the conventional fuel cell.
  • the catalyst layer becomes thin, so that the mass transfer resistance in the catalyst layer is reduced, so that the supply of the reaction gas and the removal of the generated water can be smoothed, and the resistance by the ion transfer in the catalyst layer is remarkable.
  • there is an advantage to increase the electrode activity while the smaller the absolute amount of the catalyst, the lower the active point of the reaction can not perform the chemical reaction required for the fuel cell as a whole may reduce the electrode performance.
  • the polymer electrolyte membrane has a high reaction surface area, the contact resistance between the catalyst layer and the electrolyte membrane is reduced and the hydrogen ion migration resistance is reduced, so that a small amount of catalyst is used.
  • the performance of the battery can be improved. If the amount of platinum coated on the film is less than the above range, the reaction active point may decrease, resulting in a decrease in battery performance. When the amount of the platinum coated on the membrane is less than the above range, the process cost may increase.
  • the use of the membrane electrode assembly prepared by the method of directly coating the catalyst layer using the polymer electrolyte membrane according to the present invention can greatly improve the performance of the electrode, and even with a small amount of catalyst, the performance of the fuel cell Can be significantly improved.
  • the fuel cell may be manufactured by constructing a conjugate composed of an electrolyte membrane-electrode-gas diffusion layer in the form of a Teflon-treated porous carbon paper or a carbon cloth that serves as a gas diffusion layer on both sides of the membrane electrode assembly.
  • a hierarchical microstructure 10 having a diameter of 800 nm, 20 ⁇ m, and 500 ⁇ m formed in steps on a 50 ⁇ m-thick Nafion film in steps of 120 ° C. and a pressure of 10 to 20 kg / cm 2 was formed.
  • the polymer electrolyte membrane 20 having a multiscale is produced.
  • a scanning microscope (SEM) photograph of the prepared polymer electrolyte membrane is shown in FIG. 3.
  • the prepared polymer electrolyte membrane was put in 3% by weight of hydrogen peroxide water and boiled at a temperature of about 80 ° C. for 1 hour, and then washed in boiling ultrapure water.
  • the polymer electrolyte membrane was placed in a 0.5 M sulfuric acid solution, boiled at a temperature of about 80 ° C. for 1 hour, washed again in ultrapure water, and dried to obtain a polymer.
  • the surface of the electrolyte membrane was pretreated.
  • the surface of the polymer electrolyte membrane was pretreated in the same manner as in Example 1 except for using a Nafion membrane having a pattern of 800 nm in diameter.
  • the surface of the polymer electrolyte membrane was pretreated in the same manner as in Example 1 except for using a Nafion membrane having a pattern having a diameter of 20 ⁇ m.
  • the surface of the polymer electrolyte membrane was pretreated in the same manner as in Example 1 except for using a Nafion membrane having a pattern of 500 ⁇ m in diameter.
  • the surface of the polymer electrolyte membrane was pretreated in the same manner as in Example 1 except for using a flat Nafion membrane without hierarchical microstructures.
  • Pt / C platinum catalyst
  • the catalyst slurry was coated on both surfaces of the pretreated polymer electrolyte membranes prepared in Example 1 and Comparative Example 1 by spraying, and then dried at room temperature for 12 hours to prepare a membrane electrode assembly.
  • a fuel cell was manufactured by bonding a gas diffusion membrane (SGL 35 BC) to the membrane electrode assembly.
  • the prepared conjugate was measured for CV (Cyclic Voltammogram) by the following method for the evaluation of the electrochemical activity of the fuel cell.
  • Humidified air can be supplied for electrolyte hydration.
  • the gas provided for humidification may include all of nitrogen, oxygen, hydrogen, and an inert gas, and preferably hydrogen and nitrogen gas having a relative humidity of 100% may be supplied.
  • the CV measurement step hydrogen is supplied to the cathode (anode) and nitrogen is supplied to the cathode (cathode), and the electrochemical activity by redox is measured at a boosting speed of 100 mV / s in a voltage range of 0.05 V to 1.2 V.
  • the electrochemically active surface (EAS) can be measured.
  • the measurement may be performed at room temperature. The measured results are shown in FIG. 5.
  • the electrochemically active area can be calculated using the equation of Equation 1 from the measurement result.
  • the unit cell was manufactured, and power density evaluation was performed on 80 degreeC temperature conditions.
  • FIG. 6 The power density evaluation results are shown in FIG. 6 and Table 1.
  • FIG. 6 The power density evaluation results are shown in FIG. 6 and Table 1.
  • a unit cell was prepared and the impedance (Electrochemical Impedance Spectroscopy: EIS) (IM6, Zahner) of the unit cell was measured.
  • EIS Electrochemical Impedance Spectroscopy
  • the EIS measurement of the unit cell was carried out in the range of 0.1 Hz to 100 Hz with an amplitude of 10 mV at a voltage of 0.6 V.
  • the resistance value and the constant phase element (CPE) for each element were calculated using the equivalent circuit shown in FIG. 8 and are shown in Table 2.
  • the CPE is a parameter representing the wettability according to the temporal change of the electrode.
  • CPE constant phase element of cathode (anode)
  • the fuel cell using the polymer electrolyte membrane of the present invention includes a polymer electrolyte membrane having a significantly increased thickness and surface area, thereby increasing the electrochemically active reaction area and reducing ion resistance. It can be improved, and these effects have resulted in improved performance of the fuel cell.
  • a polymer electrolyte membrane having a thin thickness and an increased specific surface area is used to manufacture a membrane electrode assembly of a fuel cell, whereby a electrode having excellent performance can be manufactured using a small amount of catalyst, thereby producing a fuel cell with improved performance. can do.
  • the average membrane thickness may be reduced to reduce its ion conductivity and resistance characteristics, and the problem of deterioration of mechanical properties due to the reduction of the membrane thickness may also be solved.
  • the catalyst layer is directly coated on the polymer electrolyte membrane whose surface area is increased by the hierarchical structure, thereby reducing the contact resistance between the catalyst layer and the electrolyte membrane.
  • the hydrogen ion transfer resistance is reduced, so that the performance of the battery can be improved even with a small amount of catalyst.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

La présente invention concerne une membrane à électrolyte polymère formant une structure hiérarchique de deux couches ou plus, et un procédé de fabrication de la membrane à électrolyte polymère par utilisation d'une structure hiérarchique ayant un motif qui est symétrique de la structure hiérarchique de la membrane à électrolyte polymère. La membrane à électrolyte polymère est prévue pour un élément de stockage d'énergie et peut lui être utilement appliquée en ce que non seulement la surface utile est accrue et l'épaisseur moyenne de la membrane est réduite afin de réduire la résistance au mouvement ionique en son sein et d'améliorer ainsi la conductivité ionique, mais en outre le problème de dégradation des propriétés mécaniques en raison d'une diminution de l'épaisseur de la membrane peut être résolu par la structure hiérarchique.
PCT/KR2016/000566 2015-01-20 2016-01-20 Membrane à électrolyte polymère et son procédé de fabrication WO2016117915A1 (fr)

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CN114824300A (zh) * 2022-04-25 2022-07-29 江苏昊氢世纪新能源有限公司 一种具有梯度结构催化层的燃料电池用膜电极及制备方法

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KR102312029B1 (ko) * 2019-12-16 2021-10-14 한국과학기술원 계층적 주름 구조를 갖는 전해질 막의 제조방법

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KR20140146012A (ko) * 2013-06-14 2014-12-24 주식회사 엘지화학 막 전극 접합체의 제조방법, 막 전극 접합체 및 이를 포함하는 연료전지

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JP2006179463A (ja) * 2004-11-25 2006-07-06 Nissan Motor Co Ltd 固体高分子型燃料電池
JP2014139884A (ja) * 2013-01-21 2014-07-31 Honda Motor Co Ltd 燃料電池用金属セパレータ
KR20140129721A (ko) * 2013-04-30 2014-11-07 한국에너지기술연구원 연료전지의 고분자 전해질막, 이의 제조방법 및 이를 포함하는 연료전지
KR20140146014A (ko) * 2013-06-14 2014-12-24 주식회사 엘지화학 전해질 막, 그의 제조방법 및 그를 포함하는 막 전극 접합체와 연료전지
KR20140146012A (ko) * 2013-06-14 2014-12-24 주식회사 엘지화학 막 전극 접합체의 제조방법, 막 전극 접합체 및 이를 포함하는 연료전지

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018172073A1 (fr) * 2017-03-21 2018-09-27 Robert Bosch Gmbh Ensemble électrode à membrane pem, pile pem et procédé de fabrication d'un ensemble électrode à membrane pem
CN114824300A (zh) * 2022-04-25 2022-07-29 江苏昊氢世纪新能源有限公司 一种具有梯度结构催化层的燃料电池用膜电极及制备方法
CN114824300B (zh) * 2022-04-25 2023-11-03 江苏昊氢世纪新能源有限公司 一种具有梯度结构催化层的燃料电池用膜电极及制备方法

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KR101742861B1 (ko) 2017-06-01

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