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WO2018124764A1 - Ensemble membrane-électrode, son procédé de fabrication, et pile à combustible le comprenant - Google Patents

Ensemble membrane-électrode, son procédé de fabrication, et pile à combustible le comprenant Download PDF

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Publication number
WO2018124764A1
WO2018124764A1 PCT/KR2017/015630 KR2017015630W WO2018124764A1 WO 2018124764 A1 WO2018124764 A1 WO 2018124764A1 KR 2017015630 W KR2017015630 W KR 2017015630W WO 2018124764 A1 WO2018124764 A1 WO 2018124764A1
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Prior art keywords
adhesive layer
membrane
interfacial
electrode assembly
catalyst layer
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English (en)
Korean (ko)
Inventor
김준영
이진화
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Kolon Industries Inc
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Kolon Industries Inc
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Priority to CN201780040742.9A priority Critical patent/CN109417180B/zh
Priority to EP17887677.7A priority patent/EP3493311A4/fr
Priority to JP2019514019A priority patent/JP6792067B2/ja
Priority to US16/341,138 priority patent/US10923752B2/en
Priority claimed from KR1020170181852A external-priority patent/KR102258909B1/ko
Publication of WO2018124764A1 publication Critical patent/WO2018124764A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01M4/88—Processes of manufacture
    • 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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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 membrane-electrode assembly, a method for manufacturing the same, and a fuel cell including the same, wherein the membrane-electrode assembly has improved interfacial adhesion and interfacial stability between the catalyst layer and the ion exchange membrane, and thus hydrogen ion conduction performance of the membrane-electrode assembly.
  • Membrane-electrode capable of overcoming degradation issues, reduced gas permeability without increasing interfacial resistance and interfacial bonding problems, resulting in reduced hydrogen gas crossover, and improved performance and durability at high / low humid conditions
  • a fuel cell is a battery having a power generation system that directly converts chemical reaction energy such as oxidation / reduction reaction of hydrogen and oxygen contained in hydrocarbon-based fuel materials such as methanol, ethanol and natural gas into electrical energy.
  • chemical reaction energy such as oxidation / reduction reaction of hydrogen and oxygen contained in hydrocarbon-based fuel materials such as methanol, ethanol and natural gas
  • hydrocarbon-based fuel materials such as methanol, ethanol and natural gas
  • This fuel cell has a merit that it can produce a wide range of output by stacking by stacking unit cells, and has attracted attention as a small and portable portable power source because it shows an energy density of 4 to 10 times compared to a small lithium battery. have.
  • a stack that substantially generates electricity in a fuel cell is made up of several to dozens of unit cells consisting of a membrane-electrode assembly (MEA) and a separator (also called a bipolar plate).
  • MEA membrane-electrode assembly
  • separator also called a bipolar plate
  • the membrane-electrode assembly has a structure in which an anode (Anode, or fuel electrode) and a cathode (Cathode, or air electrode) are formed on both sides of an electrolyte membrane.
  • Fuel cells may be classified into alkali electrolyte fuel cells and polymer electrolyte fuel cells (PEMFCs) according to the state and type of electrolyte.
  • PEMFCs polymer electrolyte fuel cells
  • polymer electrolyte fuel cells may have a low operating temperature of less than 100 ° C.
  • polymer electrolyte fuel cells include hydrogen exchange gas fuel cells (Proton Exchange Membrane Fuel Cell, PEMFC), and direct methanol fuel cell (DMFC) using liquid methanol as fuel. Etc. can be mentioned.
  • FCV Fluel Cell Vehicle
  • the MEA for a polymer electrolyte fuel cell for FCV has technical limitations such as a decrease in MEA performance and a significant decrease in durability due to long time operation, and major MEA durability / performance degradation issues are as follows.
  • the catalyst layer and the catalyst are deteriorated by potential cycling occurring during load cycling, and the carbon carrier is supported by the high cathode potential at startup / shutdown.
  • An object of the present invention is to improve the interfacial bonding and interfacial stability between the catalyst layer and the ion exchange membrane to overcome the problem of deterioration of hydrogen ion conduction performance of the membrane-electrode assembly, the gas permeability is reduced without increasing the interfacial resistance and interfacial bonding problems It is to provide a membrane-electrode assembly in which gas crossover is reduced and performance and durability in high temperature / low humidity conditions can be improved.
  • Another object of the present invention is to provide a method of manufacturing the membrane-electrode assembly.
  • the catalyst layer positioned on the catalyst layer, the interface with the catalyst layer is formed on the interface adhesive layer formed soaking to a depth of the catalyst layer, and is located on the interface adhesive layer, the interface adhesive layer through the An ion exchange membrane is bonded to the catalyst layer, and the interfacial adhesive layer provides a membrane-electrode assembly including a fluorine-based ionomer having an equivalent weight (EW) of 500 g / eq to 1000 g / eq.
  • EW equivalent weight
  • the membrane-electrode assembly includes a first interfacial adhesion layer and a first catalyst layer positioned on one surface of the ion exchange membrane, a second interfacial adhesion layer and a second catalyst layer positioned on the other surface of the ion exchange membrane, and the first interfacial adhesion layer, Any one selected from the group consisting of the second interfacial adhesion layer and both may be the interfacial adhesion layer, and any one selected from the group consisting of the first catalyst layer, the second catalyst layer and both may be the catalyst layer.
  • the interfacial adhesive layer may be to infiltrate any one selected from the group consisting of pores (surface recesses) formed on the surface of the catalyst layer, pores present at a predetermined depth from the surface of the catalyst layer, and both.
  • the average depth of the interfacial adhesive layer penetrating the catalyst layer may be 1% to 10% of the average thickness of the catalyst layer.
  • the average thickness of the interfacial adhesive layer may be 0.01 ⁇ m to 5 ⁇ m.
  • the interfacial adhesive layer may include a mixture of the fluorine ionomer and a hydrocarbon ionomer having an ion exchange capacity (IEC) of 0.8 meq / g to 4.0 meq / g.
  • IEC ion exchange capacity
  • the weight ratio of the fluorine-based ionomer and the hydrocarbon-based ionomer may be 20: 1 to 1:20.
  • the interfacial adhesive layer may further include nano powder having an average particle diameter of 1 nm to 50 nm.
  • the interfacial adhesive layer may include 0.1 wt% to 20 wt% of the nanopowder based on the total weight of the interfacial adhesive layer.
  • the nano powder may be any one selected from the group consisting of an ionic conductor, a radical scavenger, an oxygen evolution reaction (OER) catalyst, and a mixture thereof.
  • the ion conductor is SnO 2 , fumed silica, clay, alumina, mica, zeolite, phosphotungstic acid, silicon tungstic acid ), Zirconium hydrogen phosphate, and any one hydrophilic inorganic additive selected from the group consisting of a mixture thereof.
  • the radical scavengers are cerium, tungsten, ruthenium, palladium, silver, rhodium, cerium, zirconium, yttrium, manganese, molybdenum, lead, vanadium, titanium, ionic forms thereof, oxide forms thereof, salt forms thereof and their It may be any one selected from the group consisting of a mixture.
  • the oxygen generation reaction catalyst may be any one platinum-based catalyst selected from the group consisting of platinum, gold, palladium, rhodium, iridium, ruthenium, osmium, platinum alloys, alloys thereof, and mixtures thereof.
  • the interface adhesive layer is An interface with the catalyst layer penetrates to a depth of the catalyst layer, wherein the interface adhesive layer includes a fluorine-based ionomer having an equivalent weight (EW) of 500 g / eq to 1000 g / eq. It provides a manufacturing method.
  • EW equivalent weight
  • the interfacial adhesive layer may be formed by spray coating the composition for forming the interfacial adhesive layer on the catalyst layer.
  • the interfacial adhesive layer may include a mixture of the fluorine ionomer and a hydrocarbon ionomer having an ion exchange capacity (IEC) of 0.8 meq / g to 4.0 meq / g.
  • IEC ion exchange capacity
  • the interfacial adhesive layer may further include nano powder having a particle diameter of 1 nm to 50 nm.
  • a fuel cell including the membrane-electrode assembly.
  • the membrane-electrode assembly of the present invention can overcome the problem of deterioration of hydrogen ion conduction performance of the membrane-electrode assembly by improving the interfacial adhesion and interfacial stability between the catalyst layer and the ion exchange membrane, and the gas permeability without increasing the interfacial resistance and interfacial bonding problems. Reduced hydrogen gas crossover can be reduced, and performance and durability in high temperature / low humid conditions can be improved.
  • FIG. 1 is a schematic view showing an interface structure of an ion exchange membrane, an interface adhesive layer, and a catalyst layer of a membrane-electrode assembly according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing the overall configuration of a fuel cell according to an embodiment of the present invention.
  • Example 3 is a graph showing the hydrogen gas permeability measured in Experimental Example 2 of the present invention.
  • Membrane electrode assembly is located on the catalyst layer, the catalyst layer, an interface adhesive layer formed by the interface with the catalyst layer penetrates to a depth of the catalyst layer, and is located on the interface adhesive layer, the interface adhesive layer It includes an ion exchange membrane bonded to the catalyst layer via a.
  • FIG. 1 is a schematic diagram showing an interface structure of an ion exchange membrane, an adhesive layer, and a catalyst layer in a membrane-electrode assembly according to an embodiment of the present invention.
  • an interfacial adhesion layer 20 is interposed between the ion exchange membrane 10 of the membrane-electrode assembly and the catalyst layer 30 including the catalyst particles 31, and the catalyst particles 31.
  • the interface between the catalyst layer 30 and the interfacial adhesion layer 20 made of) has a form penetrated between the catalyst particles 31 of the catalyst layer 30.
  • the membrane-electrode assembly may further include an electrode substrate 40 on the outer side of the catalyst layer 30.
  • the membrane-electrode assembly includes a first interfacial adhesive layer and a first catalyst layer positioned on one surface of the ion exchange membrane 10, a second interfacial adhesive layer and a second catalyst layer positioned on the other surface of the ion exchange membrane 10, Any one selected from the group consisting of the first interfacial adhesive layer, the second interfacial adhesive layer, and both of them is the interfacial adhesive layer 20, and is selected from the group consisting of the first catalyst layer, the second catalyst layer, and both. Any one of which may be the catalyst layer 30.
  • the first catalyst layer may be a cathode catalyst layer
  • the second catalyst layer may be an anode catalyst layer.
  • the interfacial adhesive layer 20 permeates any one selected from the group consisting of pores (surface recesses) formed on the surface of the catalyst layer 30, pores present at a predetermined depth from the surface of the catalyst layer 30, and both. For example, it can be formed while filling them.
  • the interfacial adhesive layer 20 fills all empty spaces between the catalyst particles 31 and the ion exchange membrane 10 to maximize the contact area between the catalyst particles 31 and the ion exchange membrane 10. can do. There are no voids between the ion exchange membrane 10 and the catalyst particles 31, and an interface between the catalyst layer 30 and the interface adhesive layer 20 is formed along the surface curvature of the catalyst particles 31. Due to the increased interface area, the ion transfer path increases, and the adhesion strength between the catalyst layer 30 and the ion exchange membrane 10 may be improved.
  • the average depth of the interfacial adhesive layer 20 penetrating the catalyst layer 30 may be 1% to 10%, 2% to 5% of the average thickness of the catalyst layer 30, and the permeable interfacial adhesion layer When the average depth of (20) is in the above range, the binding effect between the catalyst layer 30 and the interfacial adhesion layer 20 is high and the output performance is excellent.
  • the average depth of the catalyst layer 30 or the average thickness of the catalyst layer 30 may be an average value of the depth or the thickness measured with respect to the entirety of the catalyst layer 30, or at one cross section of the catalyst layer 30. It may be an average value per unit length (eg cm).
  • The% (length%) is a percentage value of a value obtained by dividing the average penetration depth of the interfacial adhesive layer 20 in length by the average thickness of the catalyst layer 30 in length.
  • the interfacial adhesive layer 20 may include a fluorine ionomer having an equivalent weight (EW) of 500 g / eq to 1000 g / eq, and include a fluorine ionomer having an equivalent weight of 550 g / eq to 950 g / eq. Can be.
  • the equivalent weight of the fluorine ionomer is the molecular mass of the fluorine ionomer per one ion conductive functional group contained in the fluorine ionomer.
  • the equivalent weight of the fluorine ionomer is less than 500 g / eq, the elution phenomenon of the fluorine ionomer or the permeability of the hydrogen fuel may increase, and when it exceeds 1000 g / eq, the hydrogen ion conductivity may be lowered under high temperature and low humidity conditions. have.
  • the fluorine ionomer has a cation exchange group such as protons or an anion exchange group such as hydroxy ions, carbonates or bicarbonates, and includes a fluorine-based polymer containing fluorine in the main chain; Or partially fluorinated polymers such as polystyrene-graft-ethylenetetrafluoroethylene copolymer or polystyrene-graft-polytetrafluoroethylene copolymer, and the like, and specific examples thereof include poly (perfluorosulfonic acid), Poly (perfluorocarboxylic acid), a copolymer of tetrafluoroethylene and fluorovinyl ether containing a sulfonic acid group, a defluorinated sulfide polyether ketone or a fluoropolymer comprising a mixture thereof.
  • a fluorine-based polymer containing fluorine in the main chain or partially fluorinated polymers such as polysty
  • the cation exchange group may be any one selected from the group consisting of a sulfonic acid group, a carboxyl group, a boronic acid group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, and a combination thereof, and in general, may be a sulfonic acid group or a carboxyl group.
  • the said fluorine-type ionomer can also be used individually or in mixture of 2 or more types.
  • the fluorine-based ionomer may include a mixture of appropriately fluorine-based ionomers exemplified in order to satisfy the equivalent range.
  • the interfacial adhesive layer 20 may include a mixture of the fluorine ionomer and the hydrocarbon ionomer.
  • gas permeability may be reduced without affecting interfacial bonding, thereby preventing hydrogen crossover.
  • the hydrocarbon-based ionomer may have an ion exchange capacity (IEC) of 0.8 meq / g to 4.0 meq / g, and 1.0 meq / g to 3.5 meq / g.
  • IEC ion exchange capacity
  • the ion exchange capacity of the hydrocarbon-based ionomer is within the above range, it is possible to improve the performance of the membrane-electrode assembly without deteriorating the conductivity of hydrogen ions under high temperature / low humidification conditions.
  • the ion exchange capacity of the hydrocarbon-based ionomer is less than 0.8 meq / g, it is possible to reduce the migration of hydrogen ions under high temperature and low humidity conditions, and when it exceeds 4.0 meq / g, the interface and transfer resistance may be increased according to the humidity. have.
  • the weight ratio of the fluorine-based ionomer and the hydrocarbon-based ionomer may be 20: 1 to 1:20, and 1: 1 to 1:10. Can be.
  • the weight ratio of the fluorine-based ionomer and the hydrocarbon-based ionomer is within the above range, hydrogen crossover may be reduced, and interfacial bonding may be increased to improve performance and lifespan of the membrane-electrode assembly.
  • the weight ratio of the hydrocarbon-based ionomer is less than 1, it may be difficult to express the effect of reducing the hydrogen fuel permeability, and when it exceeds 20, the ionomer blend may be unevenly distributed and the resistance of the electrolyte membrane may be greatly increased.
  • the hydrocarbon-based ionomer has a cation exchange group such as proton or an anion exchange group such as hydroxy ion, carbonate or bicarbonate, and has benzimidazole, polyamide, polyamideimide, polyimide, polyacetal, polyethylene, Polypropylene, acrylic resin, polyester, polysulfone, polyether, polyetherimide, polyester, polyethersulfone, polyetherimide, polycarbonate, polystyrene, polyphenylene sulfide, polyether ether ketone, polyether ketone, poly It may include a hydrocarbon-based polymer such as arylether sulfone, polyphosphazene or polyphenylquinoxaline, and specific examples thereof include sulfonated polyimide (S-PI) and sulfonated polyaryl ether sulfone (sulfonated).
  • S-PI sulfonated polyimide
  • S-PI sulfonated polyimi
  • S-PAES polyarylethersulfone
  • SPEEK sulfonated polyetheretherketone
  • SPBI sulfonated polybenzimidazole
  • S-PSU sulfonated polysulfone
  • S-PS sulfonated polystyrene
  • Polyphosphazene sulfonated Polyquinoxaline, sulfonated polyketone, sulfonated polyphenylene oxide, sulfonated polyethersulfone polyether sulfone, sulfonated polyether ketone, sulfonated polyphenylene sulfone, sulfonated polyphenylene sulfide, sulfonated polyphenylene sulfide sulfone (sulfonated polyphenylene sulfide sulfone), sulfonated polyphenylene sulfonated polyphenylene sulfone), sul
  • interfacial adhesive layer 20 may further include nano powder.
  • the nanopowder may impart functionality to the interfacial adhesive layer 20 without degrading the interfacial adhesion of the membrane-electrode assembly or increasing interfacial resistance, thereby overcoming the deterioration in durability of the membrane-electrode assembly and improving performance.
  • the nano powder may be any one selected from the group consisting of an ionic conductor, a radical scavenger, an oxygen evolution reaction (OER) catalyst, and a mixture thereof.
  • the ion conductor may be excellent in dispersibility to improve hydrogen ion conductivity of the membrane electrode assembly.
  • the ion conductor is a hydrophilic inorganic additive, specifically, SnO 2 , fumed silica, clay, alumina, mica, zeolite, phosphotungstic acid It may be any one selected from the group consisting of silicon tungstic acid, zirconium hydrogen phosphate, and mixtures thereof.
  • the ion conductor is a hydrophilic inorganic ion additive, it is possible to prevent the phenomenon of deterioration of hydrogen ion conductivity at high temperature and low humidity conditions.
  • the radical scavenger may be uniformly dispersed in the interfacial adhesion layer 20 to contribute to stabilization of the membrane-electrode assembly.
  • the radical scavenger is a transition metal ion that can decompose hydrogen peroxide into water and oxygen to inhibit the generation of hydroxy radicals, specifically cerium, tungsten, ruthenium, palladium, silver, rhodium, cerium, zirconium, yttrium, manganese. , Molybdenum, lead, vanadium, titanium, and the like, and the metals themselves, their ionic forms, their oxide forms, their salt forms, or other forms are also possible.
  • the oxygen generation reaction catalyst may be atomized / uniformly dispersed in the interfacial adhesion layer 20 to improve durability of the catalyst layer 30 through an effective water decomposition reaction.
  • the oxygen generation reaction catalyst may include a platinum-based metal active material.
  • the platinum-based metal may be used alone or in combination of two or more selected from the group consisting of platinum, gold, palladium, rhodium, iridium, ruthenium, osmium, platinum alloys, alloys thereof, and mixtures thereof.
  • the platinum alloy is Pt-Pd, Pt-Sn, Pt-Mo, Pt-Cr, Pt-W, Pt-Ru, Pt-Ru-W, Pt-Ru-Mo, Pt-Ru-Rh-Ni, Pt- Ru-Sn-W, Pt-Co, Pt-Co-Ni, Pt-Co-Fe, Pt-Co-Ir, Pt-Co-S, Pt-Co-P, Pt-Fe, Pt-Fe-Ir, Pt-Fe-S, Pt-Fe-P, Pt-Au-Co, Pt-Au-Fe, Pt-Au-Ni, Pt-Ni, Pt-Ni-Ir, Pt-Cr, Pt-Cr-Ir and It can be used individually or in mixture of 2 or more types selected from the group which consists of these combinations.
  • the catalyst particles 31 may use a metal black, or may be used by supporting the catalyst metal on a carrier.
  • the carrier may include a porous inorganic oxide such as zirconia, alumina, titania, silica, ceria, ITO, WO, SnO 2 , ZnO 2 , or a combination thereof.
  • a carbon-based carrier graphite, carbon fiber, carbon sheet, carbon black, carbon nanotube, carbon nanofiber, carbon nanowire, carbon nanoball, carbon nanohorn, carbon nano cage, graphene, stabilized carbon, activated carbon, And it may be any one selected from the group consisting of a mixture thereof.
  • the nanoparticles may have an average particle diameter of 1 nm to 50 nm and 2 nm to 35 nm.
  • the size of the nano-powder When the size of the nano-powder is in the above range, it may be uniformly dispersed in the interfacial adhesive layer 20, and may implement the membrane-electrode assembly without a large increase in resistance.
  • the average particle diameter of the nanopowder When the average particle diameter of the nanopowder is out of the above range, agglomeration phenomenon between the nanopowders or a decrease in dispersibility and phase separation may occur in the composition.
  • the interfacial adhesive layer 20 may include 0.1 wt% to 20 wt% of the nanopowder, and may include 0.5 wt% to 15 wt%, based on the total weight of the interfacial adhesive layer 20.
  • the interfacial adhesive layer 20 may be uniformly formed without the phase separation in the interfacial adhesive layer 20.
  • the content of the nano powder is less than 0.1% by weight, hydrogen ion conductivity enhancement effect, radical generation inhibiting effect and effective water decomposition reaction may be difficult to be achieved, and when the content exceeds 20% by weight, high temperature and low temperature humidity due to a decrease in dispersibility of the nano powder.
  • Output performance and durability of the membrane-electrode assembly due to reduced hydrogen ion conductivity, ionic resistance-charge transfer resistance-increased mass transfer resistance and heterogeneous water decomposition reactions under conditions Improvements may not be achieved.
  • the average thickness of the interfacial adhesive layer 20 may be 0.01 ⁇ m to 5 ⁇ m, and 0.5 ⁇ m to 3 ⁇ m.
  • the sum of the thicknesses of the catalyst layer 30, the interfacial adhesive layer 20, and the ion exchange membrane 10 may be 18 ⁇ m to 40 ⁇ m, and the interfacial adhesive layer
  • the sum of the thicknesses of the catalyst layer 30, the interfacial adhesive layer 20, and the ion exchange membrane 10 may be 2 ⁇ m to 35 ⁇ m.
  • the interfacial adhesion between the electrolyte membrane and the electrode may not be improved, and when the interfacial adhesive layer 20 exceeds 5 ⁇ m, the interface and the transfer resistance components increase to increase the performance of the membrane-electrode assembly. Can be lowered.
  • the catalyst particles 31 of the catalyst layer 30 may be any of those that can be used as a catalyst in the hydrogen oxidation reaction, oxygen reduction reaction, it is preferable to use a platinum-based metal.
  • the platinum-based metal is platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), platinum-M alloys (the M is palladium (Pd), ruthenium (Ru), iridium ( Ir), osmium (Os), gallium (Ga), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper ( Cu, silver (Ag), gold (Au), zinc (Zn), tin (Sn), molybdenum (Mo), tungsten (W), lanthanum (La) and rhodium (Rh) It may include one selected from the group consisting of) and a combination thereof, and more preferably, a combination of two or more metals selected from the platinum-based catalyst metal group may be used, but is not limited thereto. Platinum-based catalyst metals usable in the art can be used
  • the catalyst particles 31 may use a metal black, or may be used by supporting the catalyst metal on a carrier.
  • the carrier may be selected from carbon-based carriers, porous inorganic oxides such as zirconia, alumina, titania, silica, ceria, zeolite, and the like.
  • the carbon-based carrier is graphite, super P, carbon fiber, carbon sheet, carbon black, Ketjen Black, Denka black, acetylene It may be selected from acetylene black, carbon nano tube (CNT), carbon sphere, carbon ribbon, fullerene, activated carbon and one or more combinations thereof, Without being limited thereto, carriers usable in the art may be used without limitation.
  • the catalyst particles 31 may be located on the surface of the carrier, or may penetrate into the carrier while filling the internal pores of the carrier.
  • the noble metal supported on the carrier When using the noble metal supported on the carrier as a catalyst, a commercially available commercially available one may be used, or may be prepared by using a noble metal supported on the carrier.
  • the process of supporting the noble metal on the carrier is well known in the art, and thus the detailed description thereof will be easily understood by those skilled in the art.
  • the catalyst particles 31 may be contained in an amount of 20% to 80% by weight relative to the total weight of the catalyst layer 30, and when contained in less than 20% by weight, there may be a problem of deterioration of activity, and 80% by weight. If it exceeds, the active area is reduced by agglomeration of the catalyst particles 31, so that the catalytic activity may be reversely lowered.
  • the catalyst layer 30 may include a binder to improve adhesion of the catalyst layer 30 and transfer hydrogen ions.
  • an ionomer having hydrogen ion conductivity is a cation conductor having a cation exchange group such as proton or an anion conductor having an anion exchange group such as hydroxy ion, carbonate or bicarbonate.
  • the ionomer is a cation conductor having a cation exchange group such as proton or an anion conductor having an anion exchange group such as hydroxy ion, carbonate or bicarbonate.
  • the cation exchange group may be any one selected from the group consisting of sulfonic acid groups, carboxyl groups, boronic acid groups, phosphoric acid groups, imide groups, phosphonic acid groups, sulfonimide groups, sulfonamide groups, and combinations thereof, and generally sulfonic acid groups Or a carboxyl group.
  • the cation conductor includes the cation exchange group, the fluorine-based polymer containing fluorine in the main chain; Benzimidazole, polyamide, polyamideimide, polyimide, polyacetal, polyethylene, polypropylene, acrylic resin, polyester, polysulfone, polyether, polyetherimide, polyester, polyethersulfone, polyetherimide, poly Hydrocarbon-based polymers such as carbonate, polystyrene, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyaryl ether sulfone, polyphosphazene or polyphenylquinoxaline; Partially fluorinated polymers such as polystyrene-graft-ethylenetetrafluoroethylene copolymer or polystyrene-graft-polytetrafluoroethylene copolymer; Sulfone imides and the like.
  • the polymers may include a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the side chain thereof.
  • a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the side chain thereof.
  • Specific examples thereof include poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ether containing sulfonic acid groups, defluorinated sulfide polyether ketones or mixtures thereof.
  • Fluorine-based polymer comprising; Sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (SPEEK), sulfonated polybenzimine Sulfonated polybenzimidazole (SPBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene, sulfonated poly Sulfonated polyquinoxaline, sulfonated polyketone, sulfonated polyphenylene oxide, sulfonated polyether sulfone, sulfonated polyether ketone polyether ketone, sulfonated polyphenylene sulfone, sulfonated polyphenylene sulfide, sulfonated polyphenylene sulfide sulfone
  • the cation conductor may also replace H with Na, K, Li, Cs or tetrabutylammonium in the cation exchange group at the side chain end.
  • H when H is replaced with Na, NaOH is substituted during the preparation of the catalyst composition, and when tetrabutylammonium is substituted, tetrabutylammonium hydroxide is used, and K, Li, or Cs is also appropriate.
  • Substitutions may be used. Since the substitution method is well known in the art, detailed description thereof will be omitted.
  • the cationic conductor may be used in the form of a single substance or a mixture, and may also be optionally used with a nonconductive compound for the purpose of further improving adhesion to the ion exchange membrane 10. It is preferable to adjust the usage-amount so that it may be suitable for a purpose of use.
  • non-conductive compound examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and ethylene / tetrafluoro Ethylene / tetrafluoroethylene (ETFE), ethylene chlorotrifluoro-ethylene copolymer (ECTFE), polyvinylidene fluoride, copolymer of polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), dode
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • ETFE ethylene / tetrafluoro Ethylene / te
  • the anion conductors are polymers capable of transporting anions such as hydroxy ions, carbonates or bicarbonates, and the anion conductors are commercially available in the form of hydroxides or halides (generally chloride), the anion conductors being industrially purified (water purification), metal separation or catalytic processes.
  • a polymer doped with metal hydroxide may be generally used. Specifically, poly (ethersulphone) doped with metal hydroxide, polystyrene, vinyl polymer, poly (vinyl chloride), poly (vinylidene fluoride) , Poly (tetrafluoroethylene), poly (benzimidazole), poly (ethylene glycol) and the like can be used.
  • ionomer examples include nafion, aquibion and the like.
  • the ionomer may be included in an amount of 20 to 80 wt% based on the total weight of the catalyst layer 30. If the content of the ionomer is less than 20% by weight, the generated ions may not be transferred well, and if the amount of the ionomer is greater than 80% by weight, pores may be insufficient to supply hydrogen or oxygen (air). This can be reduced.
  • the membrane-electrode assembly may further include an electrode substrate 40 outside the catalyst layer 30.
  • a porous conductive substrate may be used to smoothly supply hydrogen or oxygen.
  • Typical examples thereof include a carbon film, a carbon cloth, a carbon felt, or a metal cloth (a porous film composed of a metal cloth in a fibrous state or a metal film formed on a surface of a cloth formed of polymer fibers). May be used, but is not limited thereto.
  • fluorine-based resin examples include polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride alkoxy vinyl ether, and fluorinated ethylene propylene ( Fluorinated ethylene propylene), polychlorotrifluoroethylene or copolymers thereof can be used.
  • the electrode substrate 40 may further include a microporous layer (microporous layer) for enhancing the diffusion effect of the reactants.
  • microporous layers are generally conductive powders having a small particle diameter, such as carbon powder, carbon black, acetylene black, activated carbon, carbon fiber, fullerene, carbon nanotubes, carbon nanowires, and carbon nanohorns. -horn or carbon nano ring.
  • the microporous layer is prepared by coating a composition including a conductive powder, a binder resin, and a solvent on the electrode substrate 40.
  • the binder resin may be polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride, alkoxy vinyl ether, polyvinyl alcohol, cellulose acetate Or copolymers thereof and the like can be preferably used.
  • alcohols such as ethanol, isopropyl alcohol, n-propyl alcohol, butyl alcohol, and the like, water, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like can be preferably used.
  • the coating process may be screen printing, spray coating, or coating using a doctor blade according to the viscosity of the composition, but is not limited thereto.
  • the ion exchange membrane 10 includes an ion conductor.
  • the ion conductor may be a cation conductor having a cation exchange group such as proton or an anion conductor having an anion exchange group such as hydroxy ion, carbonate or bicarbonate.
  • the cation exchange group may be any one selected from the group consisting of a sulfonic acid group, a carboxyl group, a boronic acid group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, and a combination thereof, and in general, may be a sulfonic acid group or a carboxyl group. have.
  • the cation conductor includes the cation exchange group, the fluorine-based polymer containing fluorine in the main chain; Benzimidazole, polyamide, polyamideimide, polyimide, polyacetal, polyethylene, polypropylene, acrylic resin, polyester, polysulfone, polyether, polyetherimide, polyester, polyethersulfone, polyetherimide, poly Hydrocarbon-based polymers such as carbonate, polystyrene, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyaryl ether sulfone, polyphosphazene or polyphenylquinoxaline; Partially fluorinated polymers such as polystyrene-graft-ethylenetetrafluoroethylene copolymer or polystyrene-graft-polytetrafluoroethylene copolymer; Sulfone imides and the like.
  • the polymers may include a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the side chain thereof.
  • a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the side chain thereof.
  • Specific examples thereof include poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ether containing sulfonic acid groups, defluorinated sulfide polyether ketones or mixtures thereof.
  • Fluorine-based polymer comprising; Sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (SPEEK), sulfonated polybenzimine Sulfonated polybenzimidazole (SPBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene, sulfonated poly Sulfonated polyquinoxaline, sulfonated polyketone, sulfonated polyphenylene oxide, sulfonated polyether sulfone, sulfonated polyether ketone polyether ketone, sulfonated polyphenylene sulfone, sulfonated polyphenylene sulfide, sulfonated polyphenylene sulfide sulfone
  • hydrocarbon-based polymers excellent in ion conductivity and advantageous in terms of price can be preferably used.
  • hydrocarbon-based polymers excellent in ion conductivity and advantageous in terms of price can be preferably used.
  • the hydrocarbon-based polymer included in the hydrocarbon-based ion conductor and the hydrocarbon-based polymer included in the porous support are the same material type.
  • SPI sulfonated polyimide
  • adhesion between the hydrocarbon-based ion conductor and the porous support can be further improved. And the interface resistance can be further lowered.
  • the anion conductors are polymers capable of transporting anions such as hydroxy ions, carbonates or bicarbonates, and the anion conductors are commercially available in the form of hydroxides or halides (generally chloride), the anion conductors being industrially purified (water purification), metal separation or catalytic processes.
  • a polymer doped with metal hydroxide may be generally used. Specifically, poly (ethersulphone) doped with metal hydroxide, polystyrene, vinyl polymer, poly (vinyl chloride), poly (vinylidene fluoride) , Poly (tetrafluoroethylene), poly (benzimidazole), poly (ethylene glycol) and the like can be used.
  • the ion exchange membrane 10 may be in the form of a reinforcing membrane in which the ion conductor fills pores such as a fluorine-based porous support such as e-PTFE or a porous nanoweb support prepared by electrospinning.
  • a method of manufacturing a membrane-electrode assembly forming an interface adhesive layer 20 by applying a composition for forming an interface adhesive layer on a catalyst layer 30, and a catalyst layer on which the interface adhesive layer 20 is formed. 30 and the ion exchange membrane 10 are bonded.
  • the catalyst layer 30 is formed using the composition.
  • the solvent may be a solvent selected from the group consisting of water, a hydrophilic solvent, an organic solvent and one or more mixtures thereof.
  • the hydrophilic solvent is one selected from the group consisting of alcohols, ketones, aldehydes, carbonates, carboxylates, carboxylic acids, ethers, and amides containing, as main chain, linear, branched, saturated or unsaturated hydrocarbons having 1 to 12 carbon atoms. It may have a functional group or more, they may include an alicyclic or aromatic cyclo compound as at least part of the main chain.
  • alcohols include methanol, ethanol, isopropyl alcohol, ethoxy ethanol, n-propyl alcohol, butyl alcohol, 1,2-propanediol, 1-pentanol, 1.5-pentanediol, 1.9-nonanediol, and the like;
  • Ketones include heptanone, octanon and the like;
  • Aldehydes include benzaldehyde, tolualdehyde and the like; Examples of the ester include methylpentanoate, ethyl-2-hydroxypropanoate, and the like;
  • Carboxylic acids include pentanoic acid, heptanoic acid and the like;
  • Ethers include methoxybenzene, dimethoxypropane and the like;
  • Amides include propanamide, butylamide, dimethylacetamide, and the like.
  • the organic solvent may be selected from N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran and mixtures thereof.
  • the solvent may be contained in an amount of 80 to 95% by weight based on the total weight of the composition for forming the catalyst layer, when less than 80% by weight of the solid content is too high may cause dispersion problems due to cracks and high viscosity when coating the catalyst layer (30) And greater than 95% by weight, which may be detrimental to the catalyst layer 30 activity.
  • a catalyst layer 30 may be manufactured by coating the catalyst layer forming composition on a release film as a specific example.
  • the catalyst-dispersed catalyst layer-forming composition is continuously or intermittently transferred to a coater, and then uniformly dried at a thickness of 10 ⁇ m to 200 ⁇ m on the release film. It is preferable to apply.
  • the slot die is transferred to a coater such as a die, gravure, bar, comma coater, etc. continuously through a pump according to the viscosity of the composition for forming the catalyst layer.
  • Coating, bar coating, comma coating, screen printing, spray coating, doctor blade coating, brush, etc. may be used to dry the thickness of the catalyst layer 30 on the decal film from 10 ⁇ m to 200 ⁇ m, more preferably from 10 ⁇ m to 100 ⁇ m. Apply uniformly in ⁇ m, pass through a drying furnace maintained at a constant temperature and volatilize the solvent.
  • the composition for forming the catalyst layer When the composition for forming the catalyst layer is coated with a thickness of less than 1 ⁇ m, the activity of the catalyst may be reduced due to the small catalyst content. When the coating with a thickness of more than 200 ⁇ m, the resistance of ions and electrons may be increased to increase resistance. have.
  • the drying process may be to dry at least 12 hours at 25 °C to 90 °C.
  • the drying temperature is less than 25 °C and the drying time is less than 12 hours may cause a problem that may not form a sufficiently dried catalyst layer 30, when drying at a temperature exceeding 90 °C of the catalyst layer 30 Cracking may occur.
  • the method of applying and drying the composition for forming the catalyst layer is not limited to the above.
  • the composition for forming the interface adhesive layer is coated on the catalyst layer 30 to form the interface adhesive layer 20.
  • the composition for forming an interfacial adhesive layer includes a fluorine-based ionomer having an equivalent weight (EW) of 500 g / eq to 1000 g / eq and a solvent. Since the description of the fluorine ionomer is the same as described above, repeated descriptions thereof will be omitted.
  • EW equivalent weight
  • the composition for forming an interface adhesive layer may include the fluorine-based ionomer at a concentration of 0.1% to 30%, and may include a concentration of 1% to 20%.
  • Concentration in the context of the present invention means a percentage concentration, the percentage concentration can be obtained as a percentage of the mass of the solute to the mass of the solution.
  • the composition for forming the interfacial adhesive layer includes the fluorine-based ionomer in the concentration range, hydrogen ion conductivity and interfacial bonding may be improved without increasing interfacial resistance of the membrane-electrode assembly.
  • concentration of the fluorine ionomer is less than 0.1%, the hydrogen ion transport ability may be lowered, and when the concentration of the fluorine ionomer is greater than 30%, the ionomer distribution may be nonuniformly formed.
  • alcohols such as ethanol, isopropyl alcohol, n-propyl alcohol, butyl alcohol, water, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc. may be preferably used.
  • composition for forming an interfacial adhesive layer may include a mixture of the fluorine ionomer and a hydrocarbon ionomer having an ion exchange capacity of 0.8 meq / g to 4.0 meq / g. Since the description of the hydrocarbon-based ionomer is the same as described above, repeated description is omitted.
  • the composition for forming an interfacial adhesive layer may be prepared by mixing a dispersion of the fluorine-based ionomer at a concentration of 0.1% to 30% and a dispersion of the hydrocarbon-based ionomer at a concentration of 0.1% to 30%.
  • the composition for forming an interfacial adhesive layer may include the hydrocarbon-based ionomer at a concentration of 0.1% to 30%, and may include a concentration of 1% to 15%.
  • the composition for forming the interfacial adhesive layer includes the hydrocarbon-based ionomer in the concentration range, hydrogen ion conductivity and interfacial bonding may be improved without increasing interfacial resistance of the membrane-electrode assembly.
  • the concentration of the hydrocarbon-based ionomer is less than 0.1%, the hydrogen ion transport path may not be effectively formed, and when the concentration of the hydrocarbon-based ionomer is greater than 30%, the nonuniform distribution and resistance components of the ionomer may increase.
  • composition for forming an interface adhesive layer may further include nanoparticles having a particle diameter of 1 nm to 50 nm. Since the description of the nano-powder is the same as described above, repeated description is omitted.
  • the interfacial adhesive layer 20 may be formed by spray coating the interfacial adhesive layer forming composition on the catalyst layer 30.
  • the interfacial adhesive layer 20 does not penetrate excessively into the catalyst layer 30, but penetrates to a predetermined depth from the surface of the catalyst layer 30 and fills surface curvature. It has a soothing effect.
  • the spray method is applied to the surface of the catalyst layer 30 in a state in which some solvent is volatilized and the viscosity is increased while the composition for forming the interfacial adhesive layer is injected, so that the amount of penetration into the catalyst layer 30 is not excessive and is present on the surface.
  • the pores can be selectively filled.
  • the catalyst layer 30 and the ion exchange membrane 10 are bonded to each other via the interface adhesive layer 20.
  • the catalyst layer 30 and the release film on which the interfacial adhesive layer 20 is formed may be cut to a required size, and then bonded to the ion exchange membrane 10.
  • the method of bonding the catalyst layer 30 and the ion exchange membrane 10 through the interfacial adhesive layer 20 may be, for example, a transfer method, and the transfer method may be a metal press alone or a silicon rubber material on a metal press. It may be performed by a hot pressing method of applying heat and pressure by applying a soft plate of the same rubber material.
  • the transfer method may be performed under the conditions of 80 °C to 150 °C and 50 kgf / cm 2 to 200 kgf / cm 2 .
  • transfer of the catalyst layer 30 on a release film may not be performed properly, and when it exceeds 150 ° C., the polymer of the ion exchange membrane 10 may be There is a risk that structural modification of the catalyst layer 30 may occur, and when hot pressing under a condition exceeding 200 kgf / cm 2 , the effect of compressing the catalyst layer 30 is more effective than the transfer of the catalyst layer 30. It may get bigger and may not be able to transcribe properly.
  • a fuel cell according to another embodiment of the present invention includes the membrane-electrode assembly.
  • FIG. 2 is a schematic diagram showing the overall configuration of the fuel cell.
  • the fuel cell 200 includes a fuel supply unit 210 for supplying a mixed fuel in which fuel and water are mixed, and a reforming unit for reforming the mixed fuel to generate a reformed gas including hydrogen gas ( 220, a stack 230 in which a reformed gas including hydrogen gas supplied from the reformer 220 generates an electrical energy by causing an electrochemical reaction with an oxidant, and an oxidant in the reformer 220 and the stack. It includes an oxidant supply unit 240 for supplying to (230).
  • the stack 230 induces an oxidation / reduction reaction of a reforming gas including hydrogen gas supplied from the reformer 220 and an oxidant supplied from the oxidant supply unit 240 to generate a plurality of unit cells for generating electrical energy. Equipped.
  • Each unit cell means a cell of a unit for generating electricity, wherein the membrane-electrode assembly for oxidizing / reducing oxygen in an oxidant and a reforming gas containing hydrogen gas, and a reforming gas and an oxidant including hydrogen gas
  • a separator also referred to as a bipolar plate, hereinafter referred to as a "bipolar plate" for feeding to the membrane-electrode assembly.
  • the separator is disposed on both sides of the membrane-electrode assembly at the center. At this time, the separator plates respectively located at the outermost side of the stack may be specifically referred to as end plates.
  • the end plate of the separator plate, the pipe-shaped first supply pipe 231 for injecting the reformed gas containing hydrogen gas supplied from the reforming unit 220, and the pipe-shaped second for injecting oxygen gas The supply pipe 232 is provided, and the other end plate has a first discharge pipe 233 for discharging the reformed gas containing hydrogen gas remaining unreacted in the plurality of unit cells to the outside and the unit cell described above. Finally, the second discharge pipe 234 for discharging the remaining unreacted oxidant to the outside is provided.
  • a cathode electrode composition was prepared by dispersing by 88% by weight of PtCo / C Cathode catalyst and 12% by weight of Nafion ® / H 2 O / 2-propanol solution as a binder by stirring and ultrasonic methods.
  • the cathode electrode composition was prepared by doctor blade coating on a Teflon release film and then dried at 60 ° C. for 6 hours to prepare an anode electrode. At this time, the catalyst loading in the cathode was about 0.40 mg / cm 2 .
  • anode (Anode) Nafion ® / H 2 O / 2- propanol solution of 12 wt% to 88 wt% of the catalyst with a binder were dispersed with stirring and an ultrasonic method for the anode electrode composition was prepared.
  • the anode electrode composition prepared above was doctorblade coated on a Teflon release film, and then dried at 60 ° C. for 6 hours to prepare an anode electrode. At this time, the amount of catalyst loading in the anode was about 0.10 mg / cm 2 .
  • a composition for forming an interfacial adhesive layer was prepared, wherein 5 wt% of a fluorine ionomer poly (perfluorosulfonic acid) (PFSA) having an EW of 700 g / eq and 95 wt% of a H 2 O / 2-propanol solution was prepared.
  • PFSA fluorine ionomer poly (perfluorosulfonic acid)
  • the prepared interfacial adhesive layer-forming composition was spray-coated on the prepared electrode in an amount of 0.11 mg / cm 2 at room temperature to form an interfacial adhesive layer having a thickness of about 0.5 ⁇ m on the electrode surface.
  • Example 1 the fluorine-based ionomer PFSA having an EW of 700 g / eq when manufacturing the composition for forming the interface adhesive layer, and the thickness of the interface adhesive layer was formed in the same manner as in Example 1 except that To prepare a membrane-electrode assembly.
  • Example 1 the fluorine-based ionomer PFSA having an EW of 700 g / eq when manufacturing the composition for forming the interface adhesive layer, and the thickness of the interface adhesive layer was formed in the same manner as in Example 1 except that To prepare a membrane-electrode assembly.
  • Example 1 the fluorine-based ionomer PFSA having an EW of 950 g / eq was used to prepare the composition for forming the interfacial adhesive layer, and the thickness of the interfacial adhesive layer was about 0.5 ⁇ m. To prepare a membrane-electrode assembly.
  • Example 1 the fluorine-based ionomer PFSA having an EW of 950 g / eq was used to prepare the composition for forming the interface adhesive layer, and the thickness of the interface adhesive layer was about 1.0 ⁇ m, similar to that of Example 1 above. To prepare a membrane-electrode assembly.
  • Example 1 the fluorine-based ionomer PFSA having an EW of 950 g / eq was used to prepare the composition for forming the interfacial adhesive layer, and the thickness of the interfacial adhesive layer was about 2.0 ⁇ m, similar to that of Example 1. To prepare a membrane-electrode assembly.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 1, except that the interface adhesive layer was not formed in Example 1.
  • Example 1 except that Nafion (manufactured by Dupont) having an EW of 1100 g / eq was used to prepare the composition for forming the interface bonding layer in Example 1, and the thickness of the interface bonding layer was formed to about 1.0 ⁇ m.
  • the membrane-electrode assembly was prepared in the same manner as described above.
  • a membrane-electrode assembly was prepared in the same manner as in Example 1, except that the thickness of the interface adhesive layer was 0.005 ⁇ m when the composition for forming the interface adhesive layer was formed in Example 1.
  • the thickness of the interfacial adhesive layer was formed to 0.005 ⁇ m, performance measurement was impossible because a small amount of coated portions and a plurality of uncoated portions of the interfacial adhesive layer were present on the electrodes.
  • Example 1 the fluorine-based ionomer PFSA having an EW of 700 g / eq when manufacturing the composition for forming the interface adhesive layer, and the thickness of the interface adhesive layer was formed in the same manner as in Example 1 except that To prepare a membrane-electrode assembly.
  • a cathode electrode composition was prepared by dispersing by 88% by weight of PtCo / C Cathode catalyst and 12% by weight of Nafion ® / H 2 O / 2-propanol solution as a binder by stirring and ultrasonic methods.
  • the cathode electrode composition prepared above was doctorblade coated on a Teflon release film and then dried at 60 ° C. for 6 hours to prepare an anode electrode. At this time, the catalyst loading in the cathode was about 0.40 mg / cm 2 .
  • a composition for forming an interface adhesive layer was prepared using a fluorine / hydrocarbon ionomer blend having a weight ratio of fluorine-based ionomer PFSA having an EW of 700 g / eq and a sulfonated polyether sulfone (IEC 2.3 meq / g) ionomer blend of 1: 2.
  • the interfacial adhesion layer-forming composition included the fluorine ionomer at a concentration of 1.25%, and the hydrocarbon ionomer at a concentration of 2.5%.
  • the prepared interfacial adhesive layer-forming composition was spray-coated at room temperature on the prepared electrode to form an interfacial adhesive layer on the electrode surface.
  • the loading amount of the fluorine-based hydrocarbon ionomer blend composition was 0.13 mg / cm 2
  • the thickness of the fluorine-based hydrocarbon ion interface blend layer was about 0.5 ⁇ m.
  • the fluorine-based polyelectrolyte membrane of perfluorosulfonic acid (PFSA) having a thickness of 15 to 20 ⁇ m between the prepared cathode and anode electrode was squeezed for 3 minutes under heat and pressure at 160 ° C. and 20 kgf / cm 2.
  • PFSA perfluorosulfonic acid
  • a membrane-electrode assembly was prepared in the same manner as in Example 9 except that the thickness of the interface adhesive layer was about 1.0 ⁇ m when the composition for forming the interface adhesive layer was formed in Example 9.
  • Example 9 except for changing the weight ratio of the fluorine-based / hydrocarbon-based ionomer blend to 1: 4 and the thickness of the interfacial adhesive layer to about 0.5 ⁇ m when preparing the composition for forming the interfacial adhesive layer in Example 9 In the same manner as in the film-electrode assembly was prepared.
  • Example 9 except that the weight ratio of the fluorine / hydrocarbon-based ionomer blend is changed to 1: 4 and the thickness of the interface adhesive layer is formed to about 1.0 ⁇ m when preparing the composition for forming the interface adhesive layer in Example 9 In the same manner as in the film-electrode assembly was prepared.
  • a membrane-electrode assembly was prepared in the same manner as in Example 9 except that the thickness of the interface adhesive layer was 0.005 ⁇ m when the composition for forming the interface adhesive layer was formed in Example 9.
  • the thickness of the interfacial adhesive layer was formed to 0.005 ⁇ m, performance measurement was impossible because a small amount of coated portions and a plurality of uncoated portions of the interfacial adhesive layer were present on the electrodes.
  • Example 9 except that the weight ratio of the fluorine-based hydrocarbon ionomer blend was changed to 1: 4 and the thickness of the interfacial adhesive layer was 6 ⁇ m when the composition for forming the interfacial adhesive layer was formed. In the same manner to prepare a membrane-electrode assembly.
  • Example 1 when preparing the composition for forming the interface adhesive layer, SiO 2 nanopowder having an average particle diameter of 7 nm was added in 1 wt%, and the thickness of the interface adhesive layer was formed to about 1.0 ⁇ m. In the same manner as 1 to prepare a membrane-electrode assembly.
  • Example 1 when preparing the composition for forming the interface adhesive layer, SiO 2 nanopowder having an average particle diameter of 7 nm was added in 1 wt%, and the thickness of the interface adhesive layer was formed to about 2.0 ⁇ m. In the same manner as 1 to prepare a membrane-electrode assembly.
  • SiO 2 having an average particle diameter of 7 nm when preparing the composition for forming an interface adhesive layer in Example 1 A nano-powder was added at 5 wt% and the same procedure as in Example 1 was carried out except that the thickness of the interfacial adhesive layer was about 1.0 ⁇ m, thereby preparing a membrane-electrode assembly.
  • Example 1 The preparation of the composition for forming the interface adhesive layer in Example 1 was carried out except that the SiO 2 nanopowder having an average particle diameter of 7 nm was added in a content of 5 wt% and the thickness of the interface adhesive layer was formed to about 2.0 ⁇ m.
  • a membrane-electrode assembly was prepared in the same manner as in Example 1.
  • Example 1 The preparation of the composition for forming an interface adhesive layer in Example 1 was carried out except that SiO 2 nanopowder having an average particle diameter of 7 nm was added in a content of 0.05 wt%, and the thickness of the interface adhesive layer was formed to about 1.0 ⁇ m.
  • a membrane-electrode assembly was prepared in the same manner as in Example 1.
  • Example 1 Except for adding the nano-powder at 25% by weight when preparing the composition for forming the interface adhesive layer in Example 1 was carried out in the same manner as in Example 1.
  • a membrane-electrode assembly was prepared in the same manner as in Example 15 except that the thickness of the interface adhesive layer was formed to 0.005 ⁇ m when the composition for forming the interface adhesive layer was formed in Example 15.
  • the thickness of the interfacial adhesive layer was formed to 0.005 ⁇ m, performance measurement was impossible because a small amount of coated portions and a plurality of uncoated portions of the interfacial adhesive layer were present on the electrodes.
  • Example 1 except that 5 wt% of SiO 2 nanopowder having an average particle diameter of 7 nm was added to prepare the composition for forming the interfacial adhesive layer, and the thickness of the interfacial adhesive layer was 6 ⁇ m.
  • the membrane-electrode assembly was prepared in the same manner as described above.
  • Example 1 Except that the CeO 2 nano powder having an average particle diameter of 25 nm was added in a content of 5 wt% in Example 1, and the thickness of the interfacial adhesive layer was formed to about 1.0 ⁇ m.
  • a membrane-electrode assembly was prepared in the same manner as in Example 1.
  • Ohm resistance values were measured by comparing the alternating current impedance of 300 mA / cm 2 constant current condition of MEA single cell.
  • the x-axis is the impedance real part Z '
  • the y-axis is the impedance imaginary part Z'.
  • the value of the real part at the point where the impedance curve meets the x-axis is the ohmic resistance, which is the resistance component including the electrolyte membrane resistance and the interface resistance.
  • Example 1 0.1683 0.1955 16.2
  • Example 2 0.1829 0.1954 6.8
  • Example 3 0.2182 0.2307 5.7
  • Example 5 0.1959 0.2076 6.0
  • Comparative Example 1 0.2421 0.9426 289.3 Comparative Example 2 0.2137 0.2268 6.1
  • Example 9 0.1789 0.2132 19.2
  • Example 10 0.1985 0.2175 9.6
  • Example 12 0.2015 0.2426 20.4
  • Example 15 0.2022 0.2415 19.4
  • Example 17 0.2047 0.2468 20.6
  • Example 18 0.2360 0.2797 18.5
  • Example 19 0.2136 0.2531 18.5
  • Example 22 0.2636 0.5986 127.1
  • the membrane-electrode assembly of Comparative Example 1, in which the interfacial adhesive layer of the present invention was not introduced exhibited a significant increase in resistance after the accelerated evaluation, while the membrane-electrode assembly of the example in which the interfacial adhesive layer was introduced on the catalyst layer. Showed a low increase. Through this, it is possible to confirm the effect of improving the interfacial adhesion stability of the interfacial adhesive layer.
  • the hydrogen gas permeability was measured by linear sweep voltammetry (LSV).
  • LSV linear sweep voltammetry
  • hydrogen and air were supplied in a fully humidified state for evaluating the linear sweep voltametryl LSV, and hydrogen gas permeability was measured under a potential condition of 0.2V.
  • the membrane-electrode assembly prepared in Example 9 includes a mixture of a fluorine-based ionomer and a hydrocarbon-based ionomer in the interfacial adhesive layer, thereby comparing hydrogen gas permeability without affecting interfacial bonding. It can be seen that the film-electrode assembly prepared in Example 1 has a 35% reduction effect.
  • the membrane-electrode assembly prepared in Example 9 is significantly reduced in hydrogen gas permeability compared to the membrane-electrode assembly prepared in Comparative Example 2 including only the fluorine-based ionomer in the interface adhesive layer.
  • Example 1 1.30 0.565 Example 2 1.40 0.585 Example 3 1.35 0.555 Example 5 1.35 0.575 Comparative Example 1 1.25 0.555 Comparative Example 2 1.25 0.565 Example 8 1.20 0.515 Example 9 1.30 0.565 Example 10 1.35 0.575 Example 12 1.25 0.565 Example 14 1.05 0.505 Example 15 1.30 0.560 Example 17 1.45 0.595 Example 18 1.30 0.565 Example 19 1.25 0.550 Example 22 0.95 0.485
  • the membrane-electrode assembly prepared in Example shows superior performance compared to the membrane-electrode assembly prepared in Comparative Example. Specifically, when comparing the MEA results including the interfacial adhesive layer of the same thickness, it can be observed that the current density increases as the equivalent (EW) lower under 50% RH conditions.
  • the MEA manufactured in the Example has a higher voltage at high current density than the MEA manufactured in the Comparative Example.
  • the phenomenon that the voltage at the high current density (2.2 A / cm 2 ) increases as the equivalent EW decreases.
  • a unit cell having an electrode area of 25 cm 2 and a microporous layer on both sides were configured, and fuel cells were operated by supplying hydrogen and air passing through a humidifier to both electrodes, respectively.
  • the open circuit voltage retention rate was performed through an open circuit voltage operation at 90 ° C. and a relative humidity of 30%, and is represented by a difference between an initial open circuit voltage and an open circuit voltage after 500 hours of operation.
  • the membrane-electrode assembly prepared in Comparative Example 2 includes an interfacial adhesive layer, but the open-circuit voltage retention falls below 80% within 100 hours, but the membrane-electrode assembly prepared in Example 23 As the nano-powder is included in the interfacial adhesive layer, it can be seen that after 500 hours, the open-circuit voltage retention does not fall below 80% and maintains 95%.
  • stack 231 first supply pipe
  • second discharge pipe 240 oxidant supply unit
  • the present invention relates to a membrane-electrode assembly, a method for manufacturing the same, and a fuel cell including the same, wherein the membrane-electrode assembly has improved interfacial adhesion and interfacial stability between an electrode and an ion exchange membrane, thereby improving hydrogen ion conduction performance of the membrane-electrode assembly.
  • the degradation problem can be overcome, the gas permeability can be reduced without increasing the interfacial resistance and the interfacial bonding problem, thereby reducing the hydrogen gas crossover, and improving the performance and durability at high temperature / low humidification conditions.

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  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

La présente invention se rapporte à un ensemble membrane-électrode, à son procédé de fabrication, et à une pile à combustible le comprenant. L'ensemble membrane-électrode comprend : une couche de catalyseur ; une couche d'adhésion interfaciale disposée sur la couche de catalyseur, une interface entre la couche d'adhésion d'interface et la couche de catalyseur pénétrant à une certaine profondeur de la couche de catalyseur ; et une membrane échangeuse d'ions disposée sur la couche d'adhésion interfaciale et se liant avec la couche de catalyseur par l'intermédiaire de la couche d'adhésion interfaciale, la couche d'adhésion interfaciale contenant un ionomère à base de fluor ayant un poids équivalent (EW) de 500 g/éq à 1000 g/éq. Dans l'ensemble membrane-électrode, le problème de détérioration de la performance de conductivité d'ions hydrogène de l'ensemble membrane-électrode peut être surmonté par l'amélioration de la liaison interfaciale et de la stabilité interfaciale entre l'électrode et la membrane échangeuse d'ions ; le croisement de gaz hydrogène peut être réduit par la réduction de la perméabilité au gaz sans augmenter la résistance interfaciale et les problèmes de liaison interfaciale ; et les performances ainsi que la durabilité dans des conditions de température élevée/faible humidité peuvent être améliorées.
PCT/KR2017/015630 2016-12-29 2017-12-28 Ensemble membrane-électrode, son procédé de fabrication, et pile à combustible le comprenant Ceased WO2018124764A1 (fr)

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CN201780040742.9A CN109417180B (zh) 2016-12-29 2017-12-28 膜电极组件及其制备方法和包括该膜电极组件的燃料电池
EP17887677.7A EP3493311A4 (fr) 2016-12-29 2017-12-28 Ensemble membrane-électrode, son procédé de fabrication, et pile à combustible le comprenant
JP2019514019A JP6792067B2 (ja) 2016-12-29 2017-12-28 膜−電極アセンブリー、その製造方法、そして、これを含む燃料電池
US16/341,138 US10923752B2 (en) 2016-12-29 2017-12-28 Membrane-electrode assembly, method for manufacturing same, and fuel cell comprising same

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KR20160182363 2016-12-29
KR10-2016-0182363 2016-12-29
KR1020170181852A KR102258909B1 (ko) 2016-12-29 2017-12-28 막-전극 어셈블리, 이의 제조 방법 그리고 이를 포함하는 연료 전지
KR10-2017-0181852 2017-12-28

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JP2020149839A (ja) * 2019-03-13 2020-09-17 ダイハツ工業株式会社 膜電極接合体
CN112626539A (zh) * 2020-11-27 2021-04-09 中氢能源科技(广东)有限公司 一种用于超稳定pem析氧反应的合金电催化剂及其制备方法
CN114388858A (zh) * 2021-12-01 2022-04-22 北京嘉寓氢能源科技有限公司 一种燃料电池膜电极制备方法
WO2023105228A1 (fr) * 2021-12-08 2023-06-15 Johnson Matthey Hydrogen Technologies Limited Procédé

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CN114388858A (zh) * 2021-12-01 2022-04-22 北京嘉寓氢能源科技有限公司 一种燃料电池膜电极制备方法
WO2023105228A1 (fr) * 2021-12-08 2023-06-15 Johnson Matthey Hydrogen Technologies Limited Procédé

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