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WO2019066460A1 - Membrane à électrolyte polymère, son procédé de fabrication et ensemble membrane-électrodes la comprenant - Google Patents

Membrane à électrolyte polymère, son procédé de fabrication et ensemble membrane-électrodes la comprenant Download PDF

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Publication number
WO2019066460A1
WO2019066460A1 PCT/KR2018/011372 KR2018011372W WO2019066460A1 WO 2019066460 A1 WO2019066460 A1 WO 2019066460A1 KR 2018011372 W KR2018011372 W KR 2018011372W WO 2019066460 A1 WO2019066460 A1 WO 2019066460A1
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Prior art keywords
ion conductor
layer
group
antioxidant
polymer electrolyte
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Ceased
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PCT/KR2018/011372
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English (en)
Korean (ko)
Inventor
이동훈
김나영
박중화
이은수
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Kolon Industries Inc
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Kolon Industries Inc
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Priority claimed from KR1020180113238A external-priority patent/KR102246526B1/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Priority to JP2020535951A priority Critical patent/JP6987996B2/ja
Priority to CN201880063265.2A priority patent/CN111164813A/zh
Priority to EP18863595.7A priority patent/EP3691010A4/fr
Priority to US16/646,271 priority patent/US11444305B2/en
Publication of WO2019066460A1 publication Critical patent/WO2019066460A1/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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • 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, a method for producing the same, and a membrane-electrode assembly comprising the same, and more particularly, to a polymer electrolyte membrane having excellent stability in shape and improved resistance to radicals generated during operation, And a membrane-electrode assembly including the polymer electrolyte membrane.
  • the present invention also relates to a membrane-electrode assembly including the polymer electrolyte membrane.
  • a fuel cell is a cell having a power generation system that directly converts chemical reaction energy such as an oxidation / reduction reaction of hydrogen and oxygen contained in a hydrocarbon-based fuel material such as methanol, ethanol, and natural gas into electric energy. Due to its eco-friendly characteristics with low efficiency and low emission of pollutants, it is attracting attention as a next-generation clean energy source that can replace fossil energy.
  • Such a fuel cell has a merit that it can output a wide range of output by stacking a stack of unit cells and is attracted attention as a compact and portable portable power source because it exhibits an energy density 4 to 10 times that of a small lithium battery have.
  • the stack which substantially generates electricity in the fuel cell is formed by stacking several to several tens of unit cells made up of a membrane-electrode assembly (MEA) and a separator (also referred to as a bipolar plate)
  • MEA membrane-electrode assembly
  • separator also referred to as a bipolar plate
  • the membrane-electrode assembly generally has a structure in which an anode (anode) or a cathode (cathode) is formed on both sides of an electrolyte membrane.
  • the fuel cell can be classified into an alkali electrolyte fuel cell, a polymer electrolyte fuel cell (PEMFC) and the like depending on the state and the kind of the electrolyte.
  • the polymer electrolyte fuel cell has a low operating temperature of less than 100 ° C, Speed start-up and response characteristics, and excellent durability.
  • a proton exchange membrane fuel cell using hydrogen gas as a fuel
  • a direct methanol fuel cell using liquid methanol as fuel, And the like.
  • the membrane electrode assembly is one of the most influential components
  • the polymer electrolyte membrane is one of the key factors that have the greatest influence on the performance and the price of the MEA.
  • the polymer electrolyte membrane required for the operation of the polymer electrolyte fuel cell has high hydrogen ion conductivity, chemical stability, low fuel permeability, high mechanical strength, low water content, and excellent dimensional stability.
  • the conventional polymer electrolyte membrane tends to be difficult to normally exhibit high performance under a certain temperature and relative humidity environment, especially at high / low humidification conditions. As a result, the polymer electrolyte fuel cell to which the conventional polymer electrolyte membrane is applied is limited in its use range.
  • the polymer electrolyte membrane using a perfluoropolyether polymer generally used in fuel cells for transportation has a weak resistance to radicals generated during operation and low stability to radicals, that is, a chemical stability.
  • the hydrogen ion conductivity is high due to the wide passage, but the hydrogen permeability of the fuel is high.
  • a high-durability polymer electrolyte membrane is required to overcome these shortcomings.
  • An object of the present invention is to provide a polymer electrolyte membrane which is excellent in morphological stability and has improved resistance to radicals generated during operation, has excellent stability against radicals, that is, chemical stability, Film.
  • Another object of the present invention is to provide a method for producing the polymer electrolyte membrane.
  • a porous support comprising a porous support comprising a plurality of pores, a first layer comprising a first ion conductor filling the internal voids on one side of the porous support, Wherein the first ion conductor and the second ion conductor are different from each other, and the first layer, the second layer, and the second layer include a second layer comprising a second ion conductor Wherein at least one selected from the group consisting of an organic antioxidant and an organic antioxidant is an organic antioxidant.
  • the weight of the antioxidant per unit volume of the first layer and the second layer may be different from each other.
  • the weight of the antioxidant per unit volume of the antioxidant per unit volume is 30 mg / cm 3 to 4,000 mg / cm 3
  • the weight per unit volume of the antioxidant per unit volume of the antioxidant per unit volume May be from 10 mg / cm < 3 > to 2,000 mg / cm < 3 >.
  • the polymer electrolyte membrane is disposed on one surface of the porous support and includes a first ion conductor layer including the first ion conductor and a second ion conductor layer disposed on the other surface of the porous support, 2 < / RTI > ion conductor layer.
  • the weight of the antioxidant per unit volume of the first ion conductor layer is larger than the weight of the antioxidant per unit volume of the first layer and the weight of the antioxidant per unit volume of the second ion conductor layer is less than the weight per unit volume of the second layer May be larger than the weight of the antioxidant per volume.
  • the weight of the antioxidant per unit volume may have a concentration gradient that becomes smaller or larger in the order of the first ion conductor layer, the first layer, the second layer, and the second ion conductor layer.
  • any one selected from the group consisting of the first layer, the second layer and a combination thereof comprises the organic antioxidant
  • the organic layer is formed of a material selected from the group consisting of the first layer, the second layer,
  • the layer not containing the organic antioxidant may not include the antioxidant or may include a metal-based antioxidant.
  • the organic antioxidant may be selected from the group consisting of syringic acid, vanillic acid, protocatechuic acid, coumaric acid, caffeic acid, ferulic acid, chlorogenic acid, cynarine, galic acid, and mixtures thereof.
  • the metal-based antioxidant may be any one selected from the group consisting of transition metals, noble metals, ions thereof, salts thereof, oxides thereof, and mixtures thereof capable of decomposing peroxides or radicals.
  • the first ion conductor and the second ion conductor may have different equivalent weights (EW).
  • first ion conductor and the second ion conductor are a fluorinated polymer comprising a fluorinated carbon skeleton and a side chain represented by the following Formula 1, wherein the first ion conductor and the second ion conductor have different lengths of side chains .
  • R f is independently selected from the group consisting of F, Cl and a perfluorinated alkyl group having 1 to 10 carbon atoms
  • X is an ion-exchange group
  • a is 0 to 3
  • b is a real number of 1 to 5)
  • first ion conductor and the second ion conductor are polymers comprising a hydrophilic repeating unit and a hydrophobic repeating unit, wherein the first ion conductor and the second ion conductor have a molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit They may be different from each other.
  • the molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit may be higher than the molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit of the second ion conductor.
  • the polymer electrolyte membrane may have a thickness ratio of the first ion conductor and the second ion conductor to the total thickness of the polymer electrolyte membrane of 9: 1 to 1: 9.
  • a method of preparing a porous support comprising: preparing a porous support comprising a plurality of voids; filling a first ion conductor in an inner void of one side of the porous support to form a first layer; And forming a second layer by filling a second ionic conductor in an inner cavity of the other side of the support, wherein the first ionic conductor and the second ionic conductor are different and the first layer, And any one selected from the group consisting of a combination of these includes an organic antioxidant.
  • a membrane-electrode assembly comprising an anode electrode and a cathode electrode facing each other, and a polymer electrolyte membrane according to claim 1 positioned between the anode electrode and the cathode electrode .
  • a fuel cell including the membrane-electrode assembly.
  • the polymer electrolyte membrane of the present invention is excellent in morphological stability, has improved resistance to radicals generated during operation, has excellent stability to radicals, that is, chemical stability, and has excellent ion conductivity and hydrogen permeability.
  • FIG. 1 is a cross-sectional view schematically showing a polymer electrolyte membrane according to an embodiment of the present invention.
  • FIGS. 2 and 3 are cross-sectional views schematically showing a polymer electrolyte membrane in which a plurality of polymer electrolyte membranes shown in FIG. 1 are stacked.
  • FIG. 4 is a diagram schematically showing a case where the first ion conductor layer and the second ion conductor layer contain an organic antioxidant of the same weight per unit volume.
  • FIG. 5 is a diagram schematically showing a case where the first ion conductor layer and the second ion conductor layer contain organic-based antioxidants of different weights per unit volume.
  • FIGS. 6 to 8 are diagrams schematically showing a case where the first ion conductor layer contains an organic antioxidant and the second ion conductor layer contains a metal-based antioxidant.
  • FIG. 9 is a schematic cross-sectional view of a membrane-electrode assembly according to an embodiment of the present invention.
  • FIG. 10 is a schematic diagram showing the overall configuration of a fuel cell according to an embodiment of the present invention.
  • 11 and 12 are AFM images of one side and the other side of the polymer electrolyte membrane prepared in Example 1-1 of the present invention.
  • the alkyl group includes a primary alkyl group, a secondary alkyl group and a tertiary alkyl group, and is a straight chain or branched chain alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group is a linear or branched
  • the allyl group is an allyl group having 2 to 10 carbon atoms
  • the aryl group is an aryl group having 6 to 30 carbon atoms
  • the alkoxy group is an alkoxy group having 1 to 10 carbon atoms
  • the alkylsulfonyl group is an alkyl group having 1 to 10 carbon atoms A sulfonyl group, an acyl group having 1 to 10 carbon atoms, and an aldehyde group having 1 to 10 carbon atoms.
  • the amino group includes a primary amino group, a secondary amino group and a tertiary amino group, and a secondary amino group or a tertiary amino group is an amino group having 1 to 10 carbon atoms.
  • substituted means that hydrogen is substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a cyano group, a methyl cyano group, an alkoxy group, a nitryl group, an aldehyde group, , A carboxyl group, an acetal group, a ketone group, an alkyl group, a perfluoroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an allyl group, a benzyl group, an aryl group, a heteroaryl group, a derivative thereof, It means that one has been replaced.
  • an asterisk (*) at both ends of the formula indicates that the compound is connected to another adjacent formula.
  • an ion conductor including a repeating unit represented by one general formula not only means that it contains only a repeating unit represented by any one of the formulas included in the above general formula, But may also include repeating units represented by various types of chemical formulas.
  • the polymer electrolyte membrane according to one embodiment of the present invention comprises a porous support comprising a plurality of pores, a first layer comprising a first ion conductor filling the internal voids on one side of the porous support, And a second layer comprising a second ion conductor filling the internal voids on the other side of the first ion conductor.
  • the porous support may include a highly fluorinated polymer, preferably a perfluoropolymer, which is excellent in both thermal and chemical degradation resistance as an example.
  • the porous support can be made of polytetrafluoroethylene (PTFE) or tetrafluoroethylene and CF 2 ⁇ CFC n F 2n + 1 (n is a real number from 1 to 5) or CF 2 ⁇ CFO- (CF 2 CF (CF 3 ) O) m C n F 2n + 1 (m is a real number of 0 to 15, and n is a real number of 1 to 15).
  • PTFE polytetrafluoroethylene
  • CF 2 ⁇ CFC n F 2n + 1 CF 2 ⁇ CFC n F 2n + 1
  • CF 2 ⁇ CFO- (CF 2 CF (CF 3 ) O) m C n F 2n + 1 m is a real number of 0 to 15, and n is a real number of 1 to
  • the PTFE is commercially available and can be suitably used as the porous support.
  • a foamed polytetrafluoroethylene polymer (e-PTFE) having a microstructure of a polymer fibril or a microstructure in which nodes are connected to each other by fibrils can be suitably used as the porous support,
  • a film having a fine structure of a polymeric fibril can also be suitably used as the porous support.
  • the porous support comprising the perfluoropolymer can be produced by extrusion molding the dispersed polymerized PTFE onto a tape in the presence of a lubricant, and stretching the resulting material to form a more porous and stronger porous support. Further, the amorphous content of the PTFE may be increased by heat-treating the e-PTFE at a temperature exceeding the melting point of the PTFE (about 342 ° C).
  • the e-PTFE film prepared by the above method may have micropores and porosity having various diameters. The e-PTFE film produced by the above method may have a porosity of at least 35%, and the diameter of the micropores may be about 0.01 ⁇ to 1 ⁇ .
  • the thickness of the porous support including the perfluoropolymer may be varied, but may be, for example, 2 to 40 ⁇ , preferably 5 to 20 ⁇ . If the thickness of the porous support is less than 2 ⁇ , the mechanical strength may be significantly deteriorated. On the other hand, if the thickness exceeds 40 ⁇ , the resistance loss may increase and the weight and integration may be decreased.
  • the porous support may be a nonwoven fibrous web consisting of a plurality of randomly oriented fibers.
  • the nonwoven fibrous web is interlaid but refers to a sheet having the structure of individual fibers or filaments, but not in the same manner as a woven fabric.
  • the nonwoven fibrous web may be fabricated from a variety of materials including carding, garneting, air-laying, wet-laying, melt blowing, spunbonding, stitch bonding, and stitch bonding.
  • the fibers may comprise one or more polymeric materials, and any of those generally used as fiber-forming polymeric materials may be used, and specifically, hydrocarbon-based fiber-forming polymeric materials may be used.
  • the fiber-forming polymeric material may be a polyolefin such as polybutylene, polypropylene and polyethylene; Polyesters such as polyethylene terephthalate and polybutylene terephthalate; Polyamides (nylon-6 and nylon-6,6); Polyurethane; Polybutene; Polylactic acid; Polyvinyl alcohol; Polyphenylene sulfide; Polysulfone; A fluid crystalline polymer; Polyethylene-co-vinyl acetate; Polyacrylonitrile; Cyclic polyolefins; Polyoxymethylene; Polyolefinic thermoplastic elastomers; And combinations thereof.
  • the present invention is not limited thereto.
  • the porous support in the form of a nonwoven fibrous web, may include a nanoweb in which the nanofibers are integrated into a nonwoven fabric including a plurality of pores.
  • the nanofiber exhibits excellent chemical resistance and can be preferably used because it has hydrophobicity and has no fear of morphological change due to moisture in a high humidity environment.
  • the hydrocarbon-based polymer include nylon, polyimide, polyaramid, polyetherimide, polyacrylonitrile, polyaniline, polyethylene oxide, polyethylene naphthalate, polybutylene terephthalate, styrene butadiene rubber, polystyrene, polyvinyl chloride, Polyolefins such as polyvinyl alcohol, polyvinylidene fluoride, polyvinyl butylene, polyurethane, polybenzoxazole, polybenzimidazole, polyamideimide, polyethylene terephthalate, polyphenylene sulfide, polyethylene, polypropylene, , And mixtures thereof.
  • polyimides having superior heat resistance, chemical resistance, and shape stability can be preferably used.
  • the nano-web is a collection of nanofibers in which nanofibers produced by electrospinning are randomly arranged.
  • the nanofiber was measured for 50 fiber diameters using a scanning electron microscope (JSM6700F, JEOL), and the fiber diameter was measured to be 40 to 5000 nm It is preferable to have an average diameter. If the average diameter of the nanofibers is less than 40 nm, the mechanical strength of the porous support may be lowered. If the average diameter of the nanofibers exceeds 5,000 nm, the porosity may be significantly decreased and the thickness may be increased.
  • the thickness of the nonwoven fibrous web may be between 10 ⁇ m and 50 ⁇ m, and specifically between 15 ⁇ m and 43 ⁇ m. If the thickness of the nonwoven fibrous web is less than 10 ⁇ , the mechanical strength may be lowered. If the nonwoven fibrous web is more than 50 ⁇ , the resistance loss may increase and the weight and integration may be lowered.
  • the nonwoven fibrous web may have a basis weight of 5 mg / cm 2 to 30 mg / cm 2 . If the basis weight of the nonwoven fibrous web is less than 5 mg / cm 2 , it may be difficult to function as a porous support due to the formation of visible pores. When the basis weight of the nonwoven fibrous web is more than 30 mg / cm 2 , As shown in FIG.
  • the porosity of the porous support may be 45% or more, specifically 60% or more.
  • the porous support preferably has a porosity of 90% or less. If the porosity of the porous support exceeds 90%, the morphology stability may be lowered so that the post-process may not proceed smoothly.
  • the porosity can be calculated according to the ratio of the volume of air to the total volume of the porous support according to Equation (1).
  • the total volume can be obtained by measuring the width, length, and thickness of a rectangular sample, and calculating the air volume by subtracting the volume of the polymer inversely calculated from the density after the measurement of the mass of the sample from the total volume.
  • Porosity (%) (air volume in the porous support / total volume of the porous support) X 100
  • the polymer electrolyte membrane is a polymer electrolyte membrane in the form of a reinforced composite membrane filled with an ion conductor in an inner void of the porous support.
  • the polymer electrolyte membrane may include a first ion conductor layer located on one side of the porous support and a second ion conductor layer located on the other side of the porous support.
  • the first ion conductor layer and the second ion conductor layer may be formed as the ion conductor remaining after filling the internal voids of the porous support forms a thin film on the surface of the porous support.
  • FIG. 1 is a cross-sectional view schematically showing an example of the polymer electrolyte membrane 1. As shown in Fig.
  • the polymer electrolyte membrane 1 includes a first layer 11 including a first ion conductor 20 filling an internal space of one side of the porous support 10, And a second layer (12) comprising a second ionic conductor (30) filling the internal voids on the other side of the first layer (10).
  • the polymer electrolyte membrane 1 includes a first ion conductor layer 21 located on one side of the porous support 10 and a second ion conductor layer 31 located on the other side of the porous support 10, . ≪ / RTI >
  • the first ion conductor layer 21 may include a first ion conductor 20 and the second ion conductor layer 31 may comprise a second ion conductor 30.
  • the present invention is not limited to FIG. 1, and the pores of the porous support 10 may be filled with only the first ion conductor 20 or the second ion conductor 30.
  • the polymer electrolyte membrane 1 may be formed by laminating a plurality of the porous supports 10 including the first ion conductor 20 and the second ion conductor 30.
  • FIGS. 2 and 3 are sectional views schematically showing a polymer electrolyte membrane 1 in which a plurality of porous supports 10 are stacked.
  • the polyelectrolyte membrane 1 has a structure in which the first ion conductor 20-1 or the second ion conductor 30-1 of the first porous support 10-1 is a second ion conductor, May be stacked so as to face each other with the first ion conductor (20-2) or the second ion conductor (30-2) of the porous support (10-2). 2, the first ion conductor 20-1 of the first porous support 10-1 and the first ion conductor 20-2 of the second porous support 10-2 are connected to each other In FIG. 3, the second ion conductor 30-1 of the first porous support 10-1 is connected to the first ion of the second porous support 10-2, And the conductor 20-2 are stacked so as to face each other.
  • the first ion conductor and the second ion conductor may be different from each other.
  • the first ion conductor and the second ion conductor may have equivalent weight (EW) or ion exchange capacity (IEC) Can be different from each other.
  • the first ion conductor may have an equivalent weight (EW) of 300 g / eq to 950 g / eq, specifically 400 g / eq to 750 g / eq, EW) can be from 650 g / eq to 1500 g / eq, and more specifically from 800 g / eq to 1100 g / eq.
  • EW equivalent weight
  • the first ion conductor may have an ion exchange capacity (IEC) of 1.0 meq / g to 3.5 meq / g, specifically, 1.3 meq / g to 2.5 meq / g or less,
  • the equivalent weight (EW) may be from 0.6 meq / g to 1.6 meq / g, and more specifically from 0.9 meq / g to 1.3 meq / g.
  • the first ion conductor can exhibit a high ion conductivity efficiency, and the second ion conductor can secure the morphological stability and durability of the polymer electrolyte membrane itself while reducing the swelling property of the polymer electrolyte membrane.
  • the first ion conductor on one side of the porous support, it is possible to improve the ion conductivity and reduce the membrane resistance to improve the performance efficiency of the fuel cell, and on the other side of the porous support, By introducing an ion conductor, the shape stability of the polymer electrolyte membrane can be ensured and the durability performance of the polymer electrolyte membrane can be ensured.
  • the ratio of the thickness of the first ion conductor layer may be 10 to 200% of the total thickness of the porous support, specifically 50 to 100% of the length of the porous support, May be 10 to 200% by length, and more preferably 50 to 100% by length, based on the total thickness. If the thickness ratio of the first ion conductor layer and the second ion conductor layer is less than 10% by weight, ion conductivity may not be exhibited. If the thickness ratio exceeds 200%, the porous support may not serve as a support, Similar to the membrane, durability can be reduced.
  • the thickness ratio of the ion conductor layer on one side can be calculated by the following equation (2).
  • the thickness ratio of the first ion conductor and the second ion conductor to the whole thickness of the polymer electrolyte membrane is 9: 1 to 1: 9, and may be from 9: 1 to 6: 4, and more specifically from 8: 2 to 6: 4.
  • the thickness of the first ion conductor is thicker than the thickness of the second ion conductor in order to improve the ion conductivity of the polymer electrolyte membrane and to obtain the stability of the polymer electrolyte membrane.
  • the thickness of the first ion conductor is the sum of the thickness of the first ion conductor impregnated into the internal void of the porous support and the thickness of the first ion conductor layer.
  • the thickness of the second ion conductor is the sum of the thickness of the second ion conductor impregnated with the internal voids of the porous support and the thickness of the second ion conductor layer.
  • the first ion conductor is filled with the pores of the porous support, and on one surface of the porous support, Layer, and the second ion conductor layer may be formed on the other surface of the porous support.
  • first ion conductor and the second ion conductor may each be a cation conductor having a cation exchange group such as proton independently, or an anion conductor having an anion exchange group such as a hydroxide ion, a carbonate or a 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, a sulfonic acid fluoride group, Or a carboxyl group.
  • the cation conductor includes the cation-exchange group, and the fluorine-based polymer includes fluorine in the main chain; Polyimides, polyacetals, polyethylenes, polypropylenes, acrylic resins, polyesters, polysulfones, polyethers, polyetherimides, polyesters, polyethersulfones, polyetherimides, polyamides, polyamides, Hydrocarbon polymers such as carbonates, polystyrene, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyaryl ether sulfone, polyphosphazene or polyphenylquinoxaline; Partially fluorinated polymers such as polystyrene-graft-ethylene tetrafluoroethylene copolymer, or polystyrene-graft-polytetrafluoroethylene copolymer; Sulfonimide, and the like.
  • the polymer may include a cation exchanger selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group and derivatives thereof in the side chain, Specific examples include poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ethers containing sulfonic acid groups, defluorinated sulfated polyether ketones, or mixtures thereof
  • a fluorine-based polymer including; Sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (SPEEK), sulfonated polybenzyl ether A sulfonated polybenzimidazole (SPBI), a sulfonated polybenzimidazole (SPBI), a sulfon
  • the anionic conductor is a polymer capable of transporting an anion such as a hydroxy ion, a carbonate or a bicarbonate, and an anion conductor is commercially available in the form of a hydroxide or a halide (generally chloride) water purification, metal separation or catalytic processes.
  • an anion conductor is commercially available in the form of a hydroxide or a halide (generally chloride) water purification, metal separation or catalytic processes.
  • a metal hydroxide-doped polymer can be used as the anion conductor. Specifically, metal hydroxide doped poly (ether sulfone), polystyrene, vinyl polymer, poly (vinyl chloride), poly (vinylidene fluoride) , Poly (tetrafluoroethylene), poly (benzimidazole), poly (ethylene glycol), and the like.
  • the first ion conductor and the second ion conductor may be a fluorinated polymer, specifically, a highly fluorinated polymer including a highly fluorinated side chain, and the shape stability of the polymer electrolyte membrane may be secured
  • the lengths of the side chains may be different between the first ion conductor and the second ion conductor in order to increase the ion conductivity.
  • highly fluorinated means that at least 90 mole% of the total number of halogen and hydrogen atoms is replaced by fluorine atoms.
  • the highly fluorinated polymer comprises a polymer backbone and cyclic side chains attached to the backbone, wherein the side chains may have the ion exchange group.
  • copolymers of a first fluorinated vinyl monomer and a second fluorinated vinyl monomer having a sulfonic acid group are examples of copolymers of a first fluorinated vinyl monomer and a second fluorinated vinyl monomer having a sulfonic acid group.
  • the first fluorinated vinyl monomer may be at least one selected from the group consisting of tetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride, vinylidine fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether)
  • TFE tetrafluoroethylene
  • vinyl fluoride vinylidine fluoride
  • trifluoroethylene vinyl fluoride
  • chlorotrifluoroethylene chlorotrifluoroethylene
  • the second vinyl fluoride monomer having a sulfonic acid group may be a variety of fluorinated vinyl ethers having a sulfonic acid group.
  • the side chain may be represented by the following formula (1).
  • each of R f is independently selected from the group consisting of F, Cl, and a perfluorinated alkyl group having 1 to 10 carbon atoms
  • X is the ion exchange group, specifically, a sulfonic acid group
  • A is a real number of 0 to 3, specifically 0 to 1.
  • B is a real number of 1 to 5, specifically a real number of 2 to 4.
  • the first ion conductor may have a side chain length a + b of 2 to 6, specifically 3 to 5, and the second ion conductor may have a side chain length a + b of 4 to 8 And specifically may be more than 5 and less than 7.
  • the side chain length of the first ion conductor, a + b is less than 2
  • the structural stability of the polymer electrolyte membrane may be deteriorated and the chemical durability may be decreased due to excessive moisture absorption, and ion conductivity and performance may be lowered .
  • the side chain length a + b of the second ion conductor is less than 4, tensile strength and durability may be lowered, and if it exceeds 8, ion conductivity and performance may be deteriorated.
  • the first ion conductor and the second ion conductor are polymers comprising a hydrophilic repeating unit and a hydrophobic repeating unit, and the first ion conductor and the second ion conductor are composed of the hydrophilic repeating unit and the hydrophobic repeating unit
  • the molar ratios of the units may be different from each other.
  • At least one monomer constituting the hydrophilic repeating unit is substituted by the ion exchange group and the monomer constituting the hydrophobic repeating unit is not substituted with the ion exchange group or is substituted with a smaller number of ion exchange groups than the hydrophilic repeating unit .
  • the hydrophilic repeating unit may be composed of the monomer substituted with the ion exchange group and the monomer not substituted with the ion exchange group.
  • first ion conductor and the second ion conductor are random copolymers in which the hydrophilic repeating unit and the hydrophobic repeating unit are randomly connected to each other or a hydrophobic block composed of the hydrophilic repeating units and a hydrophobic block composed of the hydrophobic repeating units And may be a block copolymer containing hydrophobic blocks composed of blocks.
  • first ion conductor and the second ion conductor may each independently include a monomer having the hydrophilic repeating unit represented by the following formula (2).
  • each of R 111 to R 114 , R 121 to R 124 , R 131 to R 134, and R 141 to R 144 independently represents a hydrogen atom, a halogen atom, an ion conducting group, An electron donating group, and an electron withdrawing group.
  • the halogen atom may be any one selected from the group consisting of bromine, fluorine, and chlorine.
  • the ion exchange group may be any cation exchange group selected from the group consisting of a sulfonic acid group, a carboxylic acid group and a phosphoric acid group as described above, and the cation exchange group may be preferably a sulfonic acid group.
  • the ion exchange group may be an anion exchange group such as an amine group.
  • the electron donating group may be any group selected from the group consisting of an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, and an alkoxy group as an organic group for releasing electrons, May be any one selected from the group consisting of an alkylsulfonyl group, an acyl group, a halogenated alkyl group, an aldehyde group, a nitro group, a nitroso group and a nitrile group.
  • the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, an amyl group, a hexyl group, a cyclohexyl group or an octyl group
  • the halogenated alkyl group may be a trifluoromethyl group, a pentafluoroethyl group, A propyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, etc.
  • the allyl group may be a propenyl group or the like
  • the aryl group may be a phenyl group, a pentafluorophenyl group or the like.
  • the perfluoroalkyl group means a part of hydrogen atoms or an alkyl group in which all hydrogen atoms are substituted with fluorine.
  • Z 11 is a divalent organic group which may be -O- or -S-, preferably -O-.
  • the R 111 to R 114 , R 121 to R 124 , R 131 to R 134 , And at least one or more of R 141 to R 144 may be an ion exchange group.
  • hydrophilic repeating unit may be represented by the following general formula (2-1) or (2-2).
  • R 111 to R 114 , R 121 to R 124 , R 131 to R 134 , R 141 to R 144 , and Z 11 are the same as described above, do.
  • R 211 to R 214 , R 221 to R 224, and R 231 to R 234 each independently represent a hydrogen atom; A halogen atom;
  • An electron donating group selected from the group consisting of an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, and an alkoxy group;
  • an electron withdrawing group selected from the group consisting of an alkylsulfonyl group, an acyl group, a halogenated alkyl group, an aldehyde group, a nitro group, a nitroso group and a nitrile group. Since the detailed descriptions of the substituents are the same as those described above, repetitive descriptions will be omitted.
  • X 21 and X 22 may each independently be a single bond or a divalent organic group.
  • the bivalent organic group is a bivalent organic group that attracts electrons or releases electrons, and specifically includes -CO-, -SO 2 -, -CONH-, -COO-, -CR 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 - and - (CH 2 ) n -.
  • R ' is any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group and a halogenated alkyl group, and n may be a real number of 1 to 10.
  • X 21 or X 22 is a single bond, it means that the phenyl group present on both sides of X is directly connected, and a representative example thereof is a biphenyl group.
  • Z 21 is a divalent organic group, which may be -O- or -S-, and preferably -O-.
  • R 111 to R 114 , R 121 to R 124 , R 131 to R 134 , R 141 to R 144 , and Z 11 are the same as described above. do.
  • R 311 to R 314 and R 321 to R 324 each independently represent a hydrogen atom; A halogen atom; An ion conducting group; An electron donating group selected from the group consisting of an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, and an alkoxy group; And an electron withdrawing group selected from the group consisting of an alkylsulfonyl group, an acyl group, a halogenated alkyl group, an aldehyde group, a nitro group, a nitroso group and a nitrile group. Since the detailed descriptions of the substituents are the same as those described above, repetitive descriptions will be omitted.
  • X 31 represents a single bond, -CO-, -SO 2 -, -CONH-, -COO-, -CR 2 -, - (CH 2 ) n -, a cyclohexylidene group, A fluorenylidene group containing an ion-exchange group, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -O- and -S- And R 'is any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group and a halogenated alkyl group, and n may be a real number of 1 to 10. Since the detailed descriptions of the substituents are the same as those described above, repetitive descriptions will be omitted.
  • the cyclohexylidene group containing the ion-exchange group or the fluorenylidene group containing the ion-exchange group is a group in which the hydrogen of the cyclohexylidene group or the fluorenylidene group is a sulfonic acid group, a carboxylic acid group,
  • the ion exchange group is selected from the group consisting of a combination of the ion exchange groups.
  • Z 31 is a divalent organic group, which may be -O- or -S-, and preferably -O-.
  • the n 31 may be a real number of 0 to 10, preferably 0 or a real number of 1.
  • the first ion conductor and the second ion conductor may each independently include a monomer represented by the following general formula (3).
  • R 211 to R 214 , R 221 to R 224 and R 231 to R 234 , X 21 , X 22 and Z 21 have the same meanings as described above, so repetitive description will be omitted.
  • hydrophobic repeating unit may be represented by the following formula (3-1).
  • R 211 to R 214 , R 221 to R 224, and R 231 to R 234 , X 21 , X 22 and Z 21 are the same as described above, .
  • R 411 to R 414 and R 421 to R 424 each independently represent a hydrogen atom; A halogen atom; An electron donating group selected from the group consisting of an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, and an alkoxy group; And an electron withdrawing group selected from the group consisting of an alkylsulfonyl group, an acyl group, a halogenated alkyl group, an aldehyde group, a nitro group, a nitroso group and a nitrile group. Since the detailed descriptions of the substituents are the same as those described above, repetitive descriptions will be omitted.
  • X 41 represents a single bond, -CO-, -SO 2 -, -CONH-, -COO-, -CR 2 -, - (CH 2 ) n -, a cyclohexylidene group, a fluorenylidene group, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -O- and -S-, R 'represents a hydrogen atom, a halogen atom, an alkyl group and And a halogenated alkyl group, and n may be a real number of 1 to 10. Since the detailed descriptions of the substituents are the same as those described above, repetitive descriptions will be omitted.
  • Z 41 is a divalent organic group, which may be -O- or -S-, and preferably -O-.
  • N 41 may be a real number of 0 to 10, preferably 0 or a real number of 1.
  • first ion conductor and the second ion conductor may each independently include a monomer represented by the following formula (4).
  • each of R 511 to R 513 independently represents a hydrogen atom; A halogen atom; An electron donating group selected from the group consisting of an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, and an alkoxy group; And an electron withdrawing group selected from the group consisting of an alkylsulfonyl group, an acyl group, a halogenated alkyl group, an aldehyde group, a nitro group, a nitroso group and a nitrile group. Since the detailed descriptions of the substituents are the same as those described above, repetitive descriptions will be omitted.
  • Z 51 is a divalent organic group, which may be -O- or -S-, and preferably -O-.
  • hydrophobic repeating unit may be represented by the following formula (4-1).
  • R 511 to R 513 , and Z 51 are the same as those described above, and therefore, a repetitive description thereof will be omitted.
  • R 611 to R 614 and R 621 to R 624 each independently represent a hydrogen atom; A halogen atom; An electron donating group selected from the group consisting of an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, and an alkoxy group; And an electron withdrawing group selected from the group consisting of an alkylsulfonyl group, an acyl group, a halogenated alkyl group, an aldehyde group, a nitro group, a nitroso group and a nitrile group. Since the detailed descriptions of the substituents are the same as those described above, repetitive descriptions will be omitted.
  • X 61 represents a single bond, -CO-, -SO 2 -, -CONH-, -COO-, -CR 2 -, - (CH 2 ) n -, a cyclohexylidene group, a fluorenylidene group, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -O- and -S-, R 'represents a hydrogen atom, a halogen atom, an alkyl group and And a halogenated alkyl group, and n may be a real number of 1 to 10. Since the detailed descriptions of the substituents are the same as those described above, repetitive descriptions will be omitted.
  • Each Z 61 independently represents a divalent organic group, -O- or -S-, and preferably -O-.
  • N 61 may be a real number of 0 to 10, preferably 0 or a real number of 1.
  • the first ion conductor and the second ion conductor may independently have the hydrophobic repeating unit represented by the following formula (5-1).
  • R 211 to R 214, R 221 to R 224, R 231 to R 234, R 311 to R 314, R 321 to R 324, R 411 to R 414, R 421 to R 424, R 511 to R 513, R 611 To R 614 , and R 621 to R 624 are preferably substantially free of ion exchange groups.
  • R 211 to R 214, R 221 to R 224, R 231 to R 234, R 311 to R 314, R 321 to R 324, R 411 to R 414, R 421 to R 424, R 511 to R 513, R 611 To R 614 , and R 621 to R 624 are preferably substantially free of ion exchange groups.
  • the first ion conductor and the second ion conductor may each independently include a monomer having the hydrophilic repeating unit or the hydrophobic repeating unit represented by the following formula (6).
  • the first ion conductor or the second ion conductor further comprises a monomer represented by the general formula (6)
  • the first ion conductor or the second ion conductor includes a nitrogen-containing aromatic ring group in the main chain, And the interaction of the acid-base is improved. Accordingly, the first ion conductor or the second ion conductor does not cause addition reaction to the aromatic ring of the polymer electrolyte membrane or breakage of the aromatic ring due to attack of radicals formed on the cathode side during the operation of the fuel cell, By maximizing the function of the group, it is possible to improve the fuel cell operating performance in a low humidity state.
  • Z is -O- or -S-, preferably -O-.
  • Y is a divalent nitrogen-containing aromatic ring group.
  • the nitrogen-containing aromatic ring group means that at least one nitrogen atom is contained as a hetero atom in the aromatic ring.
  • other hetero atoms may include an oxygen atom, a sulfur atom, and the like.
  • the divalent nitrogen-containing aromatic ring group may be a pyrrole, thiazole, isothiazole, oxazole, isoxazole, imidazole, imidazoline, imidazolidine, pyrazole, triazine, pyridine, pyrimidine, Pyridazine, pyrazine, indole, quinoline, isoquinoline, tetrazole, tetrazine, triazole, carbazole, quinoxaline, quinazoline, indolizine, isoindole, indazole, phthalazine, naphthyridine, May be a divalent group of any nitrogen-containing aromatic ring compound selected from the group consisting of imidazole, imidazole, pyrrolidine, pyrroline, pyrazoline, pyrazolidine, piperidine, piperazine and indoline.
  • the first ion conductor and the second ion conductor may have a weight average molecular weight of 10,000 mg / cmol to 1,000,000 mg / cmol, and preferably have a weight average molecular weight of 100,000 mg / cmol to 500,000 mg / cmol. If the weight average molecular weight of the first ion conductor and the second ion conductor is less than 100,000 mg / cmol, uniform film formation may be difficult and durability may be deteriorated. When the weight average molecular weight of the first ion conductor and the second ion conductor is more than 500,000 mg / cmol, the solubility can be reduced.
  • the porous support uses a hydrocarbon-based porous support as the stability of the polymer electrolyte membrane .
  • a porous support having different properties and an ion conductor are combined, for example, when a fluorine-based porous support is combined with a hydrocarbon-based ion conductor, the ion conductor may easily be desorbed or discharged from the porous support, or impregnability may be deteriorated.
  • the first ion conductor and the second ion conductor may be prepared by preparing the hydrophilic repeating unit and the hydrophobic repeating unit, respectively, and then subjecting the hydrophilic repeating unit and the hydrophobic repeating unit to a nucleophilic substitution reaction have.
  • the hydrophilic repeating unit and the hydrophobic repeating unit may be produced by a nucleophilic substitution reaction.
  • the hydrophilic repeating unit is the repeating unit represented by the above formula (2-2)
  • It can be prepared by an aromatic nucleophilic substitution reaction of an active dihalide monomer having two components constituting the repeating unit represented by the above formula (3-1) and a dihydroxy monomer.
  • hydrophilic repeating unit is a repeating unit represented by Formula 2-2, sulfonated dichlorodiphenyl sulfone (SDCDPS), sulfonated difluorodiphenyl sulfone (SDCDPS), sulfonated dichlorodiphenyl ketone (SDCDPK), DCDPS dichlorodiphenyl sulfone), DFDPS (difluorodiphenyl sulfone or Bis- (4-fluorophenyl) -sulfone) or DCDPK (dichlorodiphenyl ketone), and the active dihydroxy monomer such as SHPF (sulfonated 9,9'- sulfonated 4,4 '- (9-Fluorenylidene biphenol) or HPF (9,9'-bis (4-hydroxyphenyl) fluorine or 4,4' - (9-Fluorenylidene biphenol) .
  • SHPF sulfonated 9,
  • 1,3-bis (4-fluorobenzoyl) benzene may be used as the active dihalide monomer.
  • DHDPS dihydroxydiphenyl sulfone
  • DHDPK dihydroxydiphenyl ketone
  • BP 4,4'-biphenol
  • hydrophobic repeating unit is a repeating unit represented by the above-mentioned formula (4-1), 2,6-difluorobenzonitrile or the like is used as the active dihalide monomer, and the active dihydroxy monomer Dihydroxydiphenyl sulfone (DHDPS), dihydroxydiphenyl ketone or dihydroxybenzophenone (DHDPK), or BP (4,4'-biphenol).
  • DHDPS Dihydroxydiphenyl sulfone
  • DHDPK dihydroxydiphenyl ketone
  • BP 4,4'-biphenol
  • both ends of the hydrophilic repeating unit are hydroxyl groups and both ends of the hydrophobic repeating unit are controlled to a halide group
  • Unit is a hydroxyl group and both ends of the hydrophilic repeating unit are controlled by a halide group
  • the hydrophilic repeating unit and the hydrophobic repeating unit can be subjected to a nucleophilic substitution reaction.
  • the nucleophilic substitution reaction may be preferably carried out in the presence of an alkaline compound.
  • the alkaline compound may be specifically exemplified by sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and the like, and either one of them or a mixture of two or more of them may be used.
  • the nucleophilic substitution reaction may be carried out in a solvent.
  • the solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl methylpyrrolidone, dimethyl sulfoxide, sulfolane, or 1,3-dimethyl-2-imidazolidinone, in the presence of an aprotic polar solvent, These may be used alone or in combination of two or more.
  • a solvent such as benzene, toluene, xylene, hexane, cyclohexane, octane, chloro benzene, dioxane dioxane, tetrahydrofuran, anisole, phenetole and the like can be coexistent.
  • the method further comprises introducing an ion exchange group into the first ion conductor and the second ion conductor.
  • the ion exchange group is a sulfonic acid group, which is a cation exchange group
  • the ion exchange group may be introduced into the ion conductor by the following two methods.
  • SDCDPS dichlorodiphenyl sulfone
  • SDCDPS sulfonated difluorodiphenyl sulfone
  • SDCDPK sulfonated dichlorodiphenyl ketone
  • 9,9'-bis 4-hydroxyphenyl) fluorine or sulfonated 4,4 '- (9-Fluorenylidene biphenol sulfonated dichlorodiphenyl sulfone
  • SDCDPK sulfonated dichlorodiphenyl ketone
  • the sulfonic acid ester group may be replaced with a monomer having an ester group to prepare the polymer having the sulfonic acid ester group, and then the sulfonic acid ester group may be de-esterified, A method of converting a group into a sulfonic acid group may be used.
  • an ion exchange group may be introduced into the hydrophilic repeating unit by preparing a polymer using a monomer not containing the ion exchange group and sulfonating the polymer using a sulfonating agent.
  • sulfuric acid can be used as the sulfonating agent.
  • another example is a method in which the polymer is reacted in the presence of an excess amount of chlorosulfonic acid (1 to 10 times, preferably 4 to 7 times, based on the total weight of the polymer) The reaction can proceed in a chlorinated solvent such as dichloromethane, chloroform, and 1,2-dichloroethane to produce an ion conductor having hydrogen ion conductivity.
  • the ion conductor may have a degree of sulfonation of 1 to 100 mol%, preferably 50 to 100 mol%. That is, the ion conductor may be a 100 mol% sulfonation site at a site that can be sulfonated, and even if the ion conductor is 100 mol% sulfonated, the dimensional stability and durability of the ion conductor may be deteriorated due to the structure of the block copolymer There is no effect. In addition, when the ion conductor has a degree of soda saturation as described above, excellent ion conductivity can be exhibited without deteriorating dimensional stability.
  • the structure control can be easily controlled and the characteristics as an ion conductor can be easily controlled.
  • the structure-controlled ion conductor can provide an ion conductor having improved ion conductivity and durability within the entire humidifying range due to the fine phase separation of the hydrophilic repeating unit and the hydrophobic repeating unit.
  • the molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit means the number of moles of the hydrophobic repeating unit contained in the first ion conductor or the second ion conductor per 1 mole of the hydrophilic repeating unit
  • the second ionic conductor may independently have a molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit of 1: 0.5 to 1:10, and may be specifically 1: 1 to 1: 5, and more specifically, 1: greater than 1.2 to 1: 5. If the molar ratio of the hydrophobic repeating units is less than 0.5, the water content increases and the dimensional stability and durability may deteriorate. If the molar ratio exceeds 10, the ion conductivity may not be exhibited.
  • the molar ratios of the hydrophilic repeating unit and the hydrophobic repeating unit may be different from each other, and even when they are composed of the same repeating units, The molar ratios of the repeating unit and the hydrophobic repeating unit may be different from each other. That is, by varying the molar ratios of the hydrophilic repeating unit and the hydrophobic repeating unit from each other, the characteristics of the expression performance can be controlled by the first ion conductor and the second ion conductor.
  • the first ion conductor may have a higher molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit than the molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit of the second ion conductor.
  • the molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit may be 1: 2 to 1: 5, specifically 1: 2 to 1: 3, and the second ion
  • the conductor may have a molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit of 1: 3 to 1: 6, and specifically 1: 3 to 1: 4, wherein the first ion conductor and the second ion Even if the molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit of the conductor is overlapped, the first ion conductor may be higher than the molar ratio of the hydrophilic repeating unit to the hydrophobic repeating unit have.
  • the first ion conductor having a relatively high molar ratio of the hydrophilic repeating unit into one surface of the porous support, it is possible to increase the ion conductivity and reduce the membrane resistance, and on the other surface of the porous support,
  • the morphology stability of the polymer electrolyte membrane can be secured by introducing the second ion conductor having a high molar ratio of the hydrophobic repeating unit.
  • any one selected from the group consisting of the first layer, the second layer, the first ion conductor layer, and the second ion conductor layer may further include an antioxidant.
  • hydroxyl radicals ( ⁇ OH - ) can be generated from hydrogen peroxide or the generated hydrogen peroxide at the cathode electrode .
  • the hydrogen peroxide or the hydroxyl radical may be generated in the anode electrode as oxygen molecules permeate the polymer electrolyte membrane. The generated hydrogen peroxide or hydroxyl radical causes degradation of the polymer electrolyte membrane or a polymer containing a sulfonic acid group contained in the catalyst electrode.
  • the antioxidant capable of decomposing the peroxide or the radical By containing the antioxidant capable of decomposing the peroxide or the radical, the generation of radicals from the peroxide can be suppressed or the generated radical can be decomposed to prevent deterioration of the polymer electrolyte membrane or the catalyst electrode, The chemical durability of the electrolyte membrane can be improved.
  • the antioxidant capable of decomposing the peroxide or radical is not particularly limited as long as it is capable of rapidly decomposing peroxides (in particular, hydrogen peroxide) or radicals (particularly hydroxyl radicals) generated during operation of the polymer electrolyte fuel cell, All are available.
  • the antioxidant capable of decomposing the peroxide or radical may be an organic antioxidant capable of decomposing the peroxide or radical, a noble metal capable of decomposing the transition metal, the peroxide or radical, , Their salt form, or their oxide form.
  • the organic antioxidant may be selected from the group consisting of syringic acid, vanillic acid, protocatechuic acid, coumaric acid, caffeic acid, caffeic acid, ferulic acid, chlorogenic acid, cynarine, galic acid, and mixtures thereof.
  • the organic antioxidant may be a compound including a resonance structure based on a double bond of a carboxylic acid, a hydroxyl group and carbon. Since the organic second antioxidant having such a structure has a molecular size effect that can not utilize a channel eluted as it has a large molecular size in comparison with ion clusters and channels in the polymer electrolyte membrane, The polymer can be prevented from being eluted through hydrogen bonding between a carboxylic acid, a hydroxyl group, and the like and a polymer in the polymer electrolyte membrane.
  • the transition metal capable of decomposing the peroxide or radical is selected from cerium (Ce), nickel (Ni), tungsten (W), cobalt (Co), chromium (Cr), zirconium (Zr) Y, Mn, Fe, Ti, V, Ir, Mo, La, and Nd. Lt; / RTI >
  • the noble metal capable of decomposing the peroxide or radical may be any one selected from the group consisting of Au, Pt, Ru, Pd and Rh.
  • the transition metal capable of decomposing the peroxide or radical or the ion of the noble metal may be at least one selected from the group consisting of cerium ion, nickel ion, tungsten ion, cobalt ion, chromium ion, zirconium ion, yttrium ion, manganese ion, iron ion, And may be any one selected from the group consisting of an ion, an iridium ion, a molybdenum ion, a lanthanum ion, a neodymium ion, a silver ion, a platinum ion, a ruthenium ion, a palladium ion and a rhodium ion. (Ce 3+ ) or a cerium tetravalent ion (Ce 4+ ).
  • the transition metal capable of decomposing the peroxide or radical or the oxide of the noble metal may be at least one selected from cerium oxide, nickel oxide, tungsten oxide, cobalt oxide, chromium oxide, zirconium oxide, yttrium oxide, manganese oxide, Vanadium, iridium oxide, molybdenum oxide, lanthanum oxide, and neodymium oxide.
  • the transition metal capable of decomposing the peroxide or radical or the salt of the noble metal may be a carbonate, a nitrate, Ammonium salts and acetylacetonate salts.
  • cerium include cerium carbonate, cerium acetate, cerium chloride, cerium acetate, cerium sulfate, cerium ammonium acetate, cerium ammonium sulfate, and the like.
  • cerium acetylacetonate as the organic metal complex salt.
  • the weight of the antioxidant per unit volume of the first layer and the second layer may be different from each other.
  • first ion conductor layer and the second ion conductor layer are formed by the first ion conductor and the second ion conductor remaining after forming the first layer and the second layer, respectively.
  • the weight of the antioxidant per unit volume of the conductor layer and the second ion conductor layer may also be different from each other.
  • the weight per unit area of the unit of the volume antioxidant is "mg / cm 3"
  • the molecule of "g” is the weight of an antioxidant
  • a denominator of "m 3” is the unit volume of the portion arbitrarily selected in the polymer electrolyte membrane to be.
  • any one selected from the group consisting of the first layer and the second layer includes only the antioxidant in either the first layer or the second layer, and the weight of the antioxidant per unit volume is not selected Can be larger than one.
  • first ion conductor layer or the second ion conductor contains the antioxidant, or any one selected from the group consisting of the first ion conductor layer and the second ion conductor layer is an antioxidant per unit volume, May be larger than the other one which is not selected.
  • the first and second layers include the ion conductor and the porous support
  • the weight of the antioxidant per unit volume of the ion conductor layer and the second ion conductor layer may be larger than the weight of the antioxidant per unit volume of the first layer and the second layer.
  • the antioxidant can move between the first layer and the second layer in accordance with the concentration gradient when forming the first layer and the second layer, for example, Is greater than the weight of the antioxidant per unit volume of the second ion conductor layer, the antioxidant of the first layer may migrate to the second layer, so that the second layer may migrate to the second ion conductor layer
  • the weight of the antioxidant per unit volume may be larger. That is, the weight of the antioxidant per unit volume may have a concentration gradient that becomes smaller or larger in the order of the first ion conductor layer, the first layer, the second layer, and the second ion conductor layer.
  • the weight of the antioxidant per unit volume of the layer having a larger weight of the antioxidant per unit volume may be 30 mg / cm 3 to 4,000 mg / cm 3 , specifically 30 g / cm 3 to 2,000 mg / cm 3 Lt; / RTI >
  • the weight of the antioxidant per unit volume of the layer having a smaller weight of the antioxidant per unit volume may be 0 mg / cm 3 to 2,000 mg / cm 3 , more specifically 10 mg / cm 3 to 1,000 mg / cm 3 Lt; / RTI > If the weight of the antioxidant per unit volume is greater than 30 mg / cm 3 , the oxidation stability may be lowered. If the weight per unit volume is more than 4,000 mg / cm 3 , And the antioxidant may be excessively discharged.
  • the problem of the elution of the antioxidant during operation of the fuel cell can be alleviated.
  • any one selected from the group consisting of the first layer, the second layer and a combination thereof may include the organic antioxidant . Accordingly, any one selected from the group consisting of the first ion conductor layer, the second ion conductor layer, and combinations thereof may include the organic antioxidant.
  • the layer not containing the organic antioxidant may not include the antioxidant or may include the metal-based antioxidant, among the first layer or the second layer.
  • the organic antioxidant-free layer of the first ion conductor layer or the second ion conductor layer may not include the antioxidant or may include the metal antioxidant.
  • FIG. 4 is a schematic view illustrating a case where the first ion conductor layer and the second ion conductor layer contain an organic antioxidant of the same weight per unit volume
  • FIG. 5 is a cross- And the ion conductor layer includes organic-based antioxidants of different weights per unit volume.
  • the first ion conductor layer 21 and the second ion conductor layer 31 may include the same amount of organic antioxidant 2 per unit volume, (11) and the second layer (12) may also contain the same weight of organic antioxidant (2) per unit volume.
  • the weight of the antioxidant per unit volume of the first ion conductor layer 21 and the second ion conductor layer 31 is preferably in the range of 1 to 10 parts by weight based on the weight of the antioxidant per unit volume of the first layer 11 and the second layer 12 Can be larger.
  • the first ion conductor layer 21 may have a larger weight of the organic antioxidant 2 per unit volume than the second ion conductor layer 31. Accordingly, the weight of the organic antioxidant (2) per unit volume of the first layer (11) may be larger than that of the second layer (12). Since the organic antioxidant 2 of the first layer 11 can be moved to the second layer 12 when the first layer 11 and the second layer 12 are formed, The second layer 12 may have a larger weight of the organic antioxidant 2 per unit volume than the second ion conductor layer 31. The weight of the organic antioxidant 2 per unit volume is less than the weight of the first ion conductor layer 21, the first layer 11, the second layer 12, the second ion conductor layer 31, In order of decreasing concentration gradient.
  • FIGS. 6 to 8 schematically show a case where the first ion conductor layer includes an organic antioxidant and the second ion conductor layer includes a metal antioxidant.
  • FIG. 6 shows a case where the weight per unit volume of the organic antioxidant is equal to that of the metal antioxidant
  • FIG. 7 shows a case where the weight per unit volume of the organic antioxidant is smaller than the weight per unit volume of the metal antioxidant 8 shows the case where the weight per unit volume of the organic antioxidant is larger than the weight per unit volume of the metal antioxidant.
  • the first ion conductor layer 21 and the second ion conductor layer 31 may each include an organic antioxidant 2 and a metal antioxidant 3 of the same weight per unit volume . Accordingly, the first layer 11 and the second layer 12 may each contain an equal weight of antioxidant per unit volume.
  • the weight of the antioxidant per unit volume of the first ion conductor layer 21 and the second ion conductor layer 31 is preferably in the range of 1 to 10 parts by weight based on the weight of the antioxidant per unit volume of the first layer 11 and the second layer 12 Can be larger.
  • the weight per unit volume of the organic-based antioxidant 2 of the first ion conductor layer 21 is greater than the weight per unit volume of the metal-based antioxidant 3 of the second ion conductor layer 31 Lt; / RTI > Accordingly, the weight per unit volume of the organic antioxidant (2) in the first layer (11) may be smaller than the weight per unit volume of the metallic antioxidant (3) in the second layer (12). Since the metal-based antioxidant 3 of the second layer 12 can be transferred to the first layer 11 when the first layer 11 and the second layer 12 are formed, The first layer 11 may have a larger weight of the antioxidant per unit volume than the first ion conductor layer 21. Accordingly, the weight of the antioxidant per unit volume becomes smaller in the order of the second ion conductor layer 31, the second layer 12, the first layer 11, and the first ion conductor layer 21 Concentration gradient.
  • the weight per unit volume of the organic antioxidant 2 of the first ion conductor layer 21 is preferably less than the weight per unit volume of the metallic antioxidant 3 of the second ion conductor layer 31 Lt; / RTI > Accordingly, the weight per unit volume of the organic antioxidant (2) of the first layer (11) may be greater than the weight per unit volume of the metallic antioxidant (3) of the second layer (12). Since the organic antioxidant 2 of the first layer 11 can be moved to the second layer 12 when the first layer 11 and the second layer 12 are formed, The second layer 12 may have a larger weight of the antioxidant per unit volume than the second ion conductor layer 31. Accordingly, the weight of the antioxidant per unit volume becomes smaller in the order of the first ion conductor layer 21, the first layer 11, the second layer 12, and the second ion conductor layer 31 Concentration gradient.
  • a method of preparing a polymer electrolyte membrane comprising: preparing a porous support having a plurality of voids; filling a first void of the porous support with a first ion conductor to form a first layer; And forming a second layer by filling a second ionic conductor in an inner cavity of the other surface of the porous support.
  • the porous support containing the plurality of voids, the first ion conductor and the second ion conductor are prepared.
  • the description of the porous support, the first ion conductor and the bi-ion conductor is the same as that described above, so repeated description will be omitted.
  • a first layer is formed by filling a first ion conductor on an inner space of one side of the porous support and a second layer is formed by filling a second ion conductor on an inner space of the other side of the porous support.
  • the first ion conductor layer may be formed on one surface of the porous support
  • the second ion conductor layer may be formed on the other surface of the porous support.
  • the first ion conductor is filled in the pores on one surface of the porous support, and the first ion conductor remaining on the one surface of the porous support is filled to form a first ion conductor layer on one surface of the porous support Filling the pores of the other surface of the porous support with the second ion conductor and filling the pores of the other surface of the porous support with the remaining second ion conductor to form a second ion conductor layer on the other surface of the porous support Respectively.
  • the present invention is not limited to this, and the pores of the porous support may be filled only with the first ion conductor, and after forming the first ion conductor layer, It is possible to form only the second ion conductor layer on the surface, and vice versa.
  • the step of filling the pores of the porous support with the first ion conductor and the second ion conductor may generally be carried out by impregnating or impregnating the porous support with a solution containing the first ion conductor or the second ion conductor .
  • the filling of the pores of the porous support with the first ion conductor and the second ion conductor may also be performed in a group consisting of a bar coating, a comma coating, a slot die, a screen printing, a spray coating, a doctor blade, a laminating, Or by any one method selected.
  • the method of manufacturing the polymer electrolyte membrane can use the existing process as it is, except that the first ion conductor and the second ion conductor are filled with one side and the other side of the porous support, respectively.
  • the first ion conductor and the second ion conductor may be filled into the porous support in the form of a solution or dispersion containing the same.
  • the solution or dispersion containing the first ion conductor or the second ion conductor may be prepared by using a commercially available ion conductor solution or dispersion and dispersing the first ion conductor or the second ion conductor in a solvent It is possible.
  • the method of dispersing the first ion conductor or the second ion conductor in a solvent can be carried out by a conventionally known method, and thus a detailed description thereof will be omitted.
  • the antioxidant may further be added to the solution or dispersion containing the first ion conductor or the second ion conductor.
  • the antioxidant may be contained only in the first ion conductor layer, or may be contained only in a part of the porous support. Further, by controlling the content of the antioxidant added to the solution or dispersion containing the first ion conductor or the second ion conductor, the content of the first layer, the second layer, the first ion conductor layer, The weight of the antioxidant per unit volume can be controlled in the 2-ion conductor layer.
  • the first layer and the second layer are in a solution state So that the antioxidant can move between the first layer and the second layer according to a concentration gradient. Accordingly, the weight of the antioxidant per unit volume may be made to have a concentration gradient that becomes smaller or larger in the order of the first ion conductor layer, the first layer, the second layer, and the second ion conductor layer.
  • a solvent selected from the group consisting of water, a hydrophilic solvent, an organic solvent and a mixture of at least one of them may be used.
  • the hydrophilic solvent may be any one selected from the group consisting of alcohols containing linear or branched saturated or unsaturated hydrocarbons having 1 to 12 carbon atoms as the main chain, isopropyl alcohol, ketone, aldehyde, carbonate, carboxylate, carboxylic acid, ether and amide , Which may contain an alicyclic or aromatic cyclic compound as at least a part of the backbone.
  • the organic solvent may be selected from N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, and mixtures thereof.
  • the step of filling the pores of the porous support with the first ion conductor or the second ion conductor may be affected by various factors such as the temperature and the time.
  • the thickness of the porous support, the concentration of the solution or dispersion containing the first ion conductor or the second ion conductor, the type of the solvent, and the like may be affected by various factors such as the temperature and the time.
  • the process may be performed at a temperature of 100 ° C or lower at any point of the solvent, and more usually at a temperature of room temperature (20 ° C) to 70 ° C or lower for about 5 minutes to 30 minutes.
  • the temperature can not be higher than the melting point of the porous support.
  • the method for producing a polymer electrolyte membrane may further include a step of preparing a plurality of the porous supports including the first ion conductor and the second ion conductor, and laminating the plurality of porous supports.
  • the laminating method can be applied when the plurality of porous supports are laminated, and the polymer electrolyte membrane having high efficiency can be manufactured by easily adjusting the thickness ratio required in the fuel cell through the lamination of the porous supports.
  • a membrane-electrode assembly including the polymer electrolyte membrane and a fuel cell.
  • the membrane-electrode assembly includes an anode electrode and a cathode electrode positioned opposite to each other, and the polymer electrolyte membrane positioned between the anode electrode and the cathode electrode.
  • the membrane-electrode assembly 100 includes the polymer electrolyte membrane 50 and the fuel cell electrodes 20 and 20 'disposed on both sides of the polymer electrolyte membrane 50 do.
  • a microporous layer (not shown) containing conductive fine particles such as carbon powder and carbon black is formed between the catalyst layers 30 and 30 'so as to facilitate diffusion of the substances in the electrode base materials 40 and 40' .
  • oxidation is performed on one side of the polymer electrolyte membrane (50) to generate hydrogen ions and electrons from the fuel that has passed through the electrode substrate (40)
  • the electrode 20 causing the reaction is referred to as an anode electrode and hydrogen ions supplied through the polymer electrolyte membrane 50 disposed on the other surface of the polymer electrolyte membrane 50 and the electrode substrate 40 '
  • the electrode 20 ' which causes a reduction reaction to generate water from the oxidant transferred to the catalyst layer 30' is referred to as a cathode electrode.
  • the catalyst layers 30 and 30 'of the anode and cathode electrodes 20 and 20' include a catalyst. Any of the catalysts which can participate in the reaction of the battery and can be used as a catalyst of a fuel cell can be used. Specifically, a platinum-based metal may be preferably used.
  • the platinum group metal may be at least one selected from the group consisting of platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), platinum-M alloy (M is palladium (Pd), ruthenium (Ir), Os, Ga, Ti, V, Cr, Mn, Fe, Co, Ni, (Rh), and at least one selected from the group consisting of Cu, Cu, Ag, Au, Zn, Sn, Mo, W, Or more), a non-platinum alloy, and combinations thereof, and more preferably, a combination of two or more metals selected from the platinum-based catalyst metal group may be used, but is limited thereto And can be used without limitation as long as it is a platinum-based catalyst metal usable in the technical field.
  • the platinum alloy may be at least one selected from the group consisting of Pt-Pd, Pt-Sn, Pt-Mo, Pt-Cr, Pt-W, Pt-Ru, Pt- Pt-Co-Fe, Pt-Co-Ni, Pt-Co-Fe, Pt, Pt-Cr, Pt-Ni, Ir, Pt-Fe-S, Pt-Fe-P, Pt-Au- Ir, and combinations thereof, or a mixture of two or more thereof.
  • the non-platinum alloy may be at least one selected from the group consisting of Ir-Fe, Ir-Ru, Ir-Os, Co-Fe, Co-Ru, Co-Os, Rh-Fe, Rh- -Ru-Os, Rh-Ru-Fe, Rh-Ru-Os, and combinations thereof, or a mixture of two or more thereof.
  • Such a catalyst may be used as the catalyst itself (black) or may be supported on a carrier.
  • the carrier may be selected from a carbon-based carrier, porous inorganic oxides such as zirconia, alumina, titania, silica, and ceria, zeolite, and the like.
  • the carbon carrier may be selected from the group consisting of graphite, super P, carbon fiber, carbon sheet, carbon black, Ketjen black, Denka black, Carbon black, carbon black, acetylene black, carbon nano tube (CNT), carbon sphere, carbon ribbon, fullerene, activated carbon, carbon nanofiber, Carbon nanoclay, carbon nanorings, ordered nano- / meso-porous carbon, carbon aerogels, mesoporous carbon, graphene, stabilized carbon, activated carbon, and May be selected from a combination of one or more of them, but the present invention is not limited thereto, and carriers usable in the art can be used without limitation.
  • the catalyst particles may be located on the surface of the carrier or may penetrate into the interior of the carrier while filling the internal pores of the carrier.
  • a noble metal supported on the support When a noble metal supported on the support is used as a catalyst, a commercially available commercially available noble metal may be used, or a noble metal supported on a support may be used. Since the process of supporting the noble metal on the carrier is well known in the art, a detailed description thereof is omitted herein, and it is easily understandable to those skilled in the art.
  • the catalyst particles may be contained in an amount of 20 wt% to 80 wt% based on the total weight of the catalyst electrodes 30 and 30 '. If the catalyst particles are contained in an amount of less than 20 wt% %, The active area may be reduced due to agglomeration of the catalyst particles, and the catalytic activity may be lowered inversely.
  • the catalyst electrodes 30 and 30 ' may include a binder for improving adhesion of the catalyst electrodes 30 and 30' and for transferring hydrogen ions.
  • a binder for improving adhesion of the catalyst electrodes 30 and 30' and for transferring hydrogen ions.
  • the binder it is preferable to use an ion conductor having ion conductivity. Since the description of the ion conductor is the same as that described above, repetitive description will be omitted.
  • the ion conductor may be used singly or as a mixture, and may also be used together with a nonconductive compound for the purpose of further improving the adhesion with the polymer electrolyte membrane 50. It is preferable to adjust the amount thereof to suit the purpose of use.
  • nonconductive compound examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene / tetrafluoro (PVdF-HFP), dodecyltrimethoxysilane (DMSO), ethylene tetrafluoroethylene (ETFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer At least one selected from the group consisting of benzene sulfonic acid and sorbitol may be used.
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • PFA tetrafluoroethylene-perflu
  • the binder may be included in an amount of 20 wt% to 80 wt% with respect to the total weight of the catalyst electrode (30, 30 '). If the content of the binder is less than 20% by weight, generated ions may not be transferred well. If the content of the binder is more than 80% by weight, it is difficult to supply hydrogen or oxygen (air) Can be reduced.
  • a porous conductive base material may be used as the electrode base material 40 or 40 'so that hydrogen or oxygen can be supplied smoothly.
  • a metal film is formed on the surface of a cloth formed of a porous film or polymer fiber composed of carbon paper, carbon cloth, carbon felt or metal cloth ) May be used, but the present invention is not limited thereto.
  • the electrode substrate 40, 40 ' is water repellent with a fluorine-based resin, because the efficiency of diffusion of the reactant by the water generated during the operation of the fuel cell can be prevented from being lowered.
  • fluorine-based resin examples include polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride alkoxyvinyl ether, fluorinated ethylene propylene ( Fluorinated ethylene propylene), polychlorotrifluoroethylene, and copolymers thereof.
  • the microporous layer may further include a microporous layer for enhancing the reactant diffusion effect in the electrode substrate 40, 40 '.
  • the microporous layer is generally composed of a conductive powder having a small particle diameter such as carbon powder, carbon black, acetylene black, activated carbon, carbon fiber, fullerene, carbon nanotube, carbon nanowire, carbon nano -horn) or a carbon nano ring.
  • the microporous layer is prepared by coating a composition comprising conductive powder, a binder resin and a solvent on the electrode substrate (40, 40 ').
  • the binder resin include polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride, alkoxyvinyl ether, polyvinyl alcohol, cellulose acetate Or a copolymer thereof, and the like can be preferably used.
  • the solvent examples include alcohols such as ethanol, isopropyl alcohol, n-propyl alcohol and butyl alcohol, water, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and tetrahydrofuran.
  • the coating process may be performed by a screen printing method, a spray coating method or a coating method using a doctor blade, depending on the viscosity of the composition, but is not limited thereto.
  • the membrane-electrode assembly 100 can be manufactured according to a conventional method for manufacturing a membrane-electrode assembly for a fuel cell, except that the polymer electrolyte membrane 50 according to the present invention is used as the polymer electrolyte membrane 50 have.
  • the fuel cell according to another embodiment of the present invention may include the membrane-electrode assembly 100.
  • FIG. 10 is a schematic diagram showing the overall configuration of the fuel cell.
  • the fuel cell 200 includes a fuel supply unit 210 for supplying mixed fuel in which fuel and water are mixed, a reforming unit for reforming the mixed fuel to generate a reformed gas containing hydrogen gas A stack 230 for generating an electric energy by generating an electrochemical reaction with a reforming gas containing hydrogen gas supplied from the reforming unit 220 with an oxidizing agent and a stack 230 for oxidizing the oxidizing agent to the reforming unit 220 and the stack 220.
  • an oxidizing agent supply unit 240 supplying the oxidizing agent to the anode 230.
  • the stack 230 includes a plurality of unit cells for generating an electric energy by inducing an oxidation / reduction reaction of a reforming gas containing hydrogen gas supplied from the reforming unit 220 and an oxidizing agent supplied from the oxidizing agent supplying unit 240 Respectively.
  • Each of the unit cells refers to a cell that generates electricity.
  • the unit cell includes a reformed gas containing hydrogen gas and the membrane-electrode assembly for oxidizing / reducing oxygen in the oxidant, a reforming gas containing hydrogen gas, (Or a bipolar plate, hereinafter referred to as a separator plate) for supplying the membrane-electrode assembly to the membrane-electrode assembly.
  • the separator is disposed on both sides of the membrane-electrode assembly with the center thereof as the center. At this time, the separator located on the outermost side of the stack may be referred to as an end plate.
  • the end plate of the separation plate is provided with a pipe-shaped first supply pipe (231) for injecting a reformed gas containing hydrogen gas supplied from the reforming unit (220), and a pipe-shaped second supply pipe 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 a second exhaust pipe 234 for discharging the remaining oxidizing agent to the outside.
  • a pipe-shaped first supply pipe (231) for injecting a reformed gas containing hydrogen gas supplied from the reforming unit (220)
  • a pipe-shaped second supply pipe A first discharge pipe 233 for discharging the reformed gas containing hydrogen gas remaining unreacted in the plurality of unit cells to the outside
  • a second exhaust pipe 234 for discharging the remaining oxidizing agent to the outside.
  • the separator, the fuel supply unit, and the oxidant supply unit constituting the electricity generating unit in the fuel cell are used in a conventional fuel cell, except that the membrane-electrode assembly 100 according to an embodiment of the present invention is used , Detailed description thereof is omitted here.
  • Bisphenol A and 1,3-bis (4-fluorobenzoyol) benzene were reacted in the presence of potassium carbonate in the presence of DMAc / Toluene co-solvent at 160 to 180 ° C for 30 hours, then discharged to purified water, washed, and then subjected to hot air drying. At this time, the carother's equation was used to control the polymerization degree of the oligomer.
  • the prepared hydrophobic repeating units and hydrophilic repeating units were reacted with DMAc / Toluene co-solvent at 160 to 180 ° C for 30 hours in the presence of potassium carbonate, and then discharged to purified water for washing, followed by hot air drying .
  • the molar ratio of the hydrophilic repeating unit: hydrophobic repeating unit of the prepared polymer was 1: 3.5.
  • the prepared polymer was dissolved in dichloromethane, slowly added to a 5-fold excess of chlorosulfonic acid / DCM solution, and stirred for 24 hours. The solution was discarded and the precipitated solid was rinsed in purified water and then subjected to hot air drying.
  • An ion conductor was produced in the same manner as in Preparation Example 1-1, except that the polymer was prepared so that the molar ratio of the hydrophilic repeating unit: hydrophobic repeating unit was 1: 2.5 in the preparation of the polymer in Production Example 1-1. Respectively.
  • the prepared hydrophobic repeating units and hydrophilic repeating units were reacted with DMAc / Toluene co-solvent at 160 to 180 ° C for 30 hours in the presence of potassium carbonate, and then discharged to purified water for washing, followed by hot air drying .
  • the molar ratio of the hydrophilic repeating unit (Y): hydrophobic repeating unit (X) of the prepared polymer was 1: 3.5.
  • the prepared polymer was dissolved in dichloromethane, slowly added to a 5-fold excess of chlorosulfonic acid / DCM solution, and stirred for 24 hours. The solution was discarded and the precipitated solid was rinsed in purified water and then subjected to hot air drying.
  • Preparation of ion conductor was carried out in the same manner as in Production Example 1-3, except that a polymer was prepared so that the molar ratio of hydrophilic repeating unit: hydrophobic repeating unit was 1: 2.5 in the preparation of the polymer in Production Example 1-3. Respectively.
  • hydrophobic repeating units and the hydrophilic repeating units were reacted at 160 to 180 ° C for 30 hours in the presence of potassium carbonate using DMAc / Toluene co-solvent, then discharged to purified water for washing, followed by hot air drying
  • a polymer represented by the following formula (7) was prepared.
  • the molar ratio of the hydrophilic repeating unit (X): hydrophobic repeating unit (Y) of the prepared polymer was 1: 3.5.
  • the prepared polymer was dissolved in dichloromethane, slowly added to a 5-fold excess of chlorosulfonic acid / DCM solution, and stirred for 24 hours. The solution was discarded and the precipitated solid was rinsed in purified water and then subjected to hot air drying.
  • the preparation of ion conductor was carried out in the same manner as in Production Example 1-5, except that the polymer was prepared so that the molar ratio of hydrophilic repeating unit: hydrophobic repeating unit was 1: 2.5 in the preparation of the polymer in Production Example 1-5. Respectively.
  • Polyamic acid was dissolved in dimethylformamide to prepare 5 L of spinning solution of 480 poise.
  • the spinning solution thus prepared was transferred to a solution tank, which was supplied through a quantitative gear pump to a spinning chamber having 20 nozzles and a high voltage of 3 kV and spinning to prepare a nanofibre precursor web. At this time, the supply amount of the solution was 1.5 ml / min.
  • the prepared nanofibrous precursor web was heat treated at 350 ° C to prepare a porous support (porosity: 40% by volume).
  • the weight per unit area of the polyimide nanofiber in the porous support was 6.8 gsm.
  • the ion conductor having the molar ratio of the hydrophilic repeating unit: hydrophobic repeating unit of 1: 3.5 prepared in Preparation Example 1-1 to the second ion conductor and the hydrophilic repeating unit prepared in Preparation Example 1-2 were used as the first ion conductor, An ion conductor solution having a molar ratio of hydrophobic repeating units of 1: 2.5 was dissolved in DMAc in an amount of 20% by weight, respectively.
  • ferulic acid was added to each ion conductor solution in an amount of 0.5 parts by weight based on 100 parts by weight of the ion conductor.
  • the polymer electrolyte membrane was prepared by impregnating the second ion conductor solution and the first ion conductor solution on the one surface and the other surface of the porous support prepared in Preparation Example 2-1, respectively.
  • an ion conductor having a relatively high molar ratio of hydrophilic repeating units prepared in Preparation Example 1-2 was impregnated on one side of the porous support, and the pores on one side of the porous support were filled
  • a first ion conductor layer was formed on one surface of the porous support, and the molar ratio of the relatively hydrophobic repeating unit prepared in Preparation Example 1-1 to the other surface of the porous support was A second ion conductor layer was formed on the other surface of the porous support by impregnating a high ion conductor to fill the pores on the other surface of the porous support to form a second layer.
  • the weight of the ion conductor was 65 mg / cm 2 .
  • the ratio of the thickness occupied by the first ion conductor produced in Production Example 1-2, in which the molar ratio of the hydrophilic repeating units was relatively high, to the entire polymer electrolyte membrane prepared was 70%, and the mole of the hydrophobic repeating unit
  • the thickness ratio is a sum of the thickness impregnated into the porous support and the thickness of the ion conductor layer formed on the surface of the porous support.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 300 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 210 mg / cm 3
  • the weight of the inhibitor was 210 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 300 mg / cm < 3 & gt ;.
  • Example 1-1 In place of the ion conductors prepared in Production Examples 1-1 and 1-2 in Example 1-1, the ion conductors prepared in Production Examples 1-3 and 1-4 and the production examples Polymer electrolyte membranes were prepared in the same manner as in Example 1-1, except that the ionic conductors prepared in Preparation Examples 1-6 and 1-6 were used.
  • Example 1-1 the ion conductor solution containing the ion conductor prepared in Preparation Example 1-1 did not contain the antioxidant, and the ion conductor including the ion conductor prepared in Preparation Example 1-2
  • the polymer electrolyte membrane was prepared in the same manner as in Example 1-1, except that ferulic acid was added in an amount of 0.5 part by weight based on 100 parts by weight of the ionic conductor.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 300 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 220 mg / cm 3
  • the oxidation per unit volume of the second layer The weight of the inhibitor was 180 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 100 mg / cm < 3 & gt ;.
  • Example 1-1 the ion conductor solution containing the ion conductor prepared in Preparation Example 1-1 contained ferulic acid in an amount of 0.5 part by weight based on 100 parts by weight of the ion conductor,
  • the polymer electrolyte membrane was prepared in the same manner as in Example 1-1, except that the ion conductor solution containing the ion conductor prepared in Example 2 did not contain an antioxidant.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 100 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 180 mg / cm 3
  • the weight of the inhibitor was 210 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 300 mg / cm < 3 & gt ;.
  • Example 1-1 the ion conductor solution containing the ion conductor prepared in Preparation Example 1-1 contained ferulic acid in an amount of 0.5 part by weight based on 100 parts by weight of the ion conductor, -2 was prepared in the same manner as in Example 1-1 except that the antioxidant, cerium nitrate, was added in an amount of 0.5 parts by weight based on 100 parts by weight of the ionic conductor.
  • the antioxidant cerium nitrate
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 300 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 210 mg / cm 3
  • the weight of the inhibitor was 210 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 300 mg / cm < 3 & gt ;.
  • the ionic conductor solution prepared by dissolving the ionic conductor prepared in Preparation Example 1-1 to 20% by weight in DMAc was impregnated with the porous substrate prepared in Preparation Example 2-1 twice for 30 minutes, For 1 hour, and dried in a vacuum of 80 ⁇ for 10 hours to prepare a polymer electrolyte membrane. At this time, the weight of the ion conductor was 65 mg / cm 2 .
  • an antioxidant such as cerium nitrate was added to the ion conductor solution in an amount of 0.1 part by weight based on 100 parts by weight of the ion conductor.
  • the ionic conductor solution prepared by dissolving the ionic conductor prepared in Preparation Example 1-2 to 20% by weight in DMAc was impregnated with the porous substrate prepared in Preparation Example 2-1 twice for 30 minutes, For 1 hour, and dried in a vacuum of 80 ⁇ for 10 hours to prepare a polymer electrolyte membrane. At this time, the weight of the ion conductor was 65 mg / cm 2 .
  • an antioxidant such as cerium nitrate was added to the ion conductor solution in an amount of 0.1 part by weight based on 100 parts by weight of the ion conductor.
  • Example 1-1 the ion conductor solution containing the ion conductor prepared in Preparation Example 1-1 and the ion conductor solution containing the ion conductor prepared in Preparation Example 1-2 were both cerium nitrate ) was added in an amount of 0.5 part by weight based on 100 parts by weight of the ionic conductor, to prepare a polymer electrolyte membrane.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 300 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 210 mg / cm 3
  • the weight of the inhibitor was 210 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 300 mg / cm < 3 & gt ;.
  • the ion exchange capacity (IEC) of the polymer electrolyte membranes prepared in Comparative Example 1-1 and Comparative Example 1-2 was evaluated by neutralization titration.
  • the ionic conductivity and dimensional stability were measured at 80 ° C and 95% relative humidity, 80 ° C and 50% relative humidity, respectively. The results are shown in Table 1 below.
  • the ionic conductivity was calculated by measuring the resistance of the membrane at 1M H 2 SO 4 .
  • the membrane resistance was calculated by the following equation (3), and the effective area of the membrane was 0.75 cm 2 .
  • R 1 is the resistance [ ⁇ ] when the film is injected
  • R 2 is the resistance [ ⁇ ] when the film is not injected.
  • the ionic conductivity was calculated by the following equation (4).
  • R is the film resistance [OMEGA .cm < 2 >] and t is the film thickness [cm].
  • the polymer electrolyte membrane thus prepared was dipped in distilled water at 80 ° C. for 24 hours, and the polymer electrolyte membrane in a wet state was taken out, and its thickness and area were measured.
  • the polymer electrolyte membrane was dried in a vacuum state at 80 ° C. for 24 hours after measuring the thickness and area, wherein the polymer electrolyte membrane thickness of the wet state (T wet) and the area (L wet) and dry thickness (T dry) and the area to the (L dry) is substituted in equation 5, and 6
  • the swelling ratio to the thickness and the swelling ratio to the area were measured.
  • Hydrophilic Hydrophobic molar ratio Film thickness ( ⁇ ⁇ ) IEC Weight average molecular weight (Mw) Moisture content (%) Conductivity (S / cm) Dimensional stability (%) RH95% RH 50% ⁇ L ⁇ T Comparative Example 1-1 1: 3.5 22-23 1.65 15 million 26 0.14 0.018 3.9 16 Comparative Example 1-2 1: 2.5 22-23 1.8 16 million 30 0.17 0.019 3.9 20
  • the polymer electrolyte membranes prepared in Comparative Example 1-1 and Comparative Example 1-2 had an ion conductor comprising a hydrocarbon-based block copolymer composed of hydrophilic repeating units and hydrophobic repeating units, And it is easy to control the properties of the block copolymer and the ion conductor by controlling the structure of the hydrophilic repeating unit and the hydrophobic repeating unit.
  • the molar ratio of the relatively hydrophilic repeating unit having a molar ratio of 1: 2.5 is 1: 3.5 . It is confirmed that the ion exchange ability and the ion conductivity are superior to the ion conductor having a high molar ratio of the hydrophobic repeating unit.
  • ionic conductors having a relatively high molar ratio of hydrophobic repeating units are advantageous, and even in the same film thickness, dimensional stability is secured and the shape stability is excellent.
  • the swelling of the polymer electrolyte membrane is a factor that greatly affects the durability.
  • the durability of the polymer electrolyte membrane on the fuel cell increases and thus the durability of the entire fuel cell can be improved.
  • FIGS. 11 and 12 AFM images of one side and the other side of the polymer electrolyte membrane prepared in Example 1-1 are shown in FIGS. 11 and 12, respectively.
  • FIG. 11 is a graph showing the relationship between the hydrophobic repeating units and the hydrophobic repeating units in the preparation of the AFM
  • FIG. 12 is a graph showing the results of the AFM analysis for one side impregnated with an ion conductor having a relatively high molar ratio of the hydrophilic repeating unit: hydrophobic repeating unit molar ratio of 1: 2.5, Image.
  • the ion conductor solution containing 30 wt% of a highly fluorinated polymer (3M Company Dyneon) having an equivalent weight (EW) of 725 as the first ion conductor and a side chain length of 0 in the formula 1 and b 4 Ferric acid was added in an amount of 0.5 part by weight based on 100 parts by weight of the ionic conductor to prepare a first ion conductor solution.
  • Ferric acid was added in an amount of 0.5 part by weight based on 100 parts by weight of the ionic conductor to prepare a first ion conductor solution.
  • a second ion conductor having an ion equivalent (EW) of 800 and a side chain having a length of 30 m < 2 > in an amount of 30% by weight of a highly fluorinated polymer (3M Company Dyneon) Ferric acid was added to the conductor solution in an amount of 0.5 part by weight based on 100 parts by weight of the ion conductor to prepare a second ion conductor solution.
  • a polymer electrolyte membrane was prepared by impregnating the ion conductor solution on one side of the PTFE porous support and the other side thereof.
  • the impregnating method first, the first ion conductor solution is impregnated on one side of the porous support to form a first layer on one side of the porous support to form a first layer, and then, on the surface of one side of the porous support Ion conductor solution is impregnated on the other surface of the porous support to form a second layer by filling the pores on the other surface of the porous support, and then the surface of the other surface of the porous support To form a second ion conductor layer.
  • the thickness ratio of the first ion conductor to the entire polymer electrolyte membrane was 70%, and the ratio of the thickness occupied by the second ion conductor was 30%.
  • the thickness ratio is a sum of the thickness impregnated into the porous support and the thickness of the ion conductor layer formed on the surface of the porous support.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 300 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 210 mg / cm 3
  • the weight of the inhibitor was 210 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 300 mg / cm < 3 & gt ;.
  • Example 2-1 the first ion conductor solution contains ferulic acid in an amount of 0.5 part by weight based on 100 parts by weight of the ion conductor, and the second ion conductor solution contains no antioxidant
  • the polymer electrolyte membrane was prepared in the same manner as in Example 2-1.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 300 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 220 mg / cm 3
  • the oxidation per unit volume of the second layer The weight of the inhibitor was 180 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 100 mg / cm < 3 & gt ;.
  • Example 2-1 the first ion conductor solution does not contain the antioxidant, and the second ion conductor solution contains 0.5 parts by weight of ferulic acid per 100 parts by weight of the ion conductor
  • the polymer electrolyte membrane was prepared in the same manner as in Example 2-1.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 100 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 180 mg / cm 3
  • the weight of the inhibitor was 220 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 300 mg / cm < 3 & gt ;.
  • Example 2-1 cerium nitrate was added in an amount of 0.5 parts by weight based on 100 parts by weight of the ionic conductor instead of ferulic acid as the antioxidant
  • the polymer electrolyte membrane was prepared in the same manner as in Example 1-1.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 300 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 210 mg / cm 3
  • the weight of the inhibitor was 210 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 300 mg / cm < 3 & gt ;.
  • the PTFE porous support was impregnated with the ion conductor solution to prepare a polymer electrolyte membrane.
  • cerium nitrate was replaced by 100 parts by weight of the ion conductor instead of ferulic acid as the antioxidant was prepared in the same manner as in Example 1-1 except that 0.5 part by weight of the polymer was used.
  • the weight of the antioxidant per unit volume of the first ion conductor layer was 300 mg / cm 3
  • the weight of the antioxidant per unit volume of the first layer was 210 mg / cm 3
  • the weight of the inhibitor was 210 mg / cm < 3 >
  • the weight of the antioxidant per unit volume of the second ion conductor layer was 300 mg / cm < 3 & gt ;.
  • the polymer electrolyte membranes prepared in the Examples and Comparative Examples were measured for the unit cell performance and the open circuit voltage (OCV) retention ratio. The results are shown in Tables 2 and 3 below.
  • the unit cell performance of the polymer electrolyte membrane was measured by the following apparatus, and its electrochemical characteristics were measured.
  • the device for measuring the energy efficiency comprises a unit cell having an electrode area of 25 cm 2 and a microporous layer on both sides in order to measure the performance of a unit cell in a fuel cell.
  • the hydrogen and air passing through the humidifier were supplied to both electrodes, and the fuel cell operation was performed.
  • the unit cell performance was measured at 65 ° C and 100% relative humidity, and the current density at 0.6 V was compared.
  • the open circuit voltage retention rate was obtained by operating the open circuit voltage at 90 °C and 30% relative humidity, and the difference between the initial open circuit voltage and the open circuit voltage after 500 hours operation.
  • Hydrophilic hydrophobic repeating unit molar ratio Film thickness ( ⁇ ⁇ ) Battery performance (mA / cm 2 ) OCV change rate (%) Comparative Example 1-1 1: 3.5 22-23 1045 95 Comparative Example 1-2 1: 2.5 22-23 1027 97 Comparative Example 1-3 1: 2.5 + 1: 3.5 1) 22-23 1013 97 Example 1-1 1: 2.5 + 1: 3.5 1) 22-23 1098 97 Examples 1-4 1: 2.5 + 1: 3.5 1) 22-23 1127 96 Examples 1-5 1: 2.5 + 1: 3.5 1) 22-23 1124 97 Examples 1-6 1: 2.5 + 1: 3.5 1) 22-23 1216 98 Nafion211 commercial membrane - 25 1184 89
  • the thickness ratio of the second ion conductor prepared in Preparation Example 1-1 in which the molar ratio of the first ion conductor and the hydrophobic repeating unit produced in Preparation Example 1-2, in which the molar ratio of the hydrophilic repeating units is relatively high 7: 3.
  • the thickness ratio is a sum of the thickness impregnated into the porous support and the thickness of the ion conductor layer formed on the surface of the porous support.
  • Example 1-1 and Comparative Example 1-3 the cell performance was relatively high when the molar ratio of the hydrophilic repeating units having relatively high ion conductivity was relatively high And the open circuit voltage retention ratio exhibited the performance of an ion conductor having a relatively high molar ratio of the hydrophobic repeating unit having a relatively excellent durability performance, and the performance of the ion conductor prepared in Comparative Example 1-1 and Comparative Example 1-2
  • the polymer electrolyte membranes prepared in Examples 1-4, Examples 1-5, and 1-6 were found to have improved system efficiency as a whole compared to the polymer electrolyte membrane.
  • the content of the antioxidant did not differ in the porous support, the first ion conductor layer and the second ion conductor layer, and the organic antioxidant was not included Accordingly, it can be confirmed that the antioxidant is eluted during operation of the fuel cell, and the efficiency is lowered.
  • the content of the antioxidant differs in the porous support, the first ion conductor layer and the second ion conductor layer,
  • the inhibitor By including the inhibitor, the problem of the elution of the antioxidant during operation of the fuel cell is alleviated, and the efficiency is further improved.
  • the content of the antioxidant did not differ in the porous support, the first ion conductor layer and the second ion conductor layer, and the organic antioxidant was not included Accordingly, it can be confirmed that the antioxidant is eluted during operation of the fuel cell, and the efficiency is lowered.
  • Second discharge pipe 240 Oxidizing agent supply part
  • the present invention relates to a polymer electrolyte membrane, a method of manufacturing the same, and a membrane-electrode assembly including the same, wherein the polymer electrolyte membrane has excellent stability in shape and stability against radicals generated during operation, The hydrogen permeability can be reduced while the ion conductivity is excellent.

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Abstract

La présente invention se rapporte à une membrane à électrolyte polymère, à son procédé de fabrication, et à un ensemble membrane-électrodes la comprenant. La membrane à électrolyte polymère comprend : un corps de support poreux comprenant de multiples pores ; une première couche comprenant un premier conducteur ionique qui remplit les pores internes d'une surface latérale du corps de support poreux ; et une seconde couche comprenant un second conducteur ionique qui remplit les pores internes de l'autre surface latérale du corps de support poreux. Le premier conducteur ionique et le second conducteur ionique sont différents l'un de l'autre. Un élément choisi dans le groupe constitué de la première couche, de la seconde couche et d'une combinaison des deux comprend un antioxydant organique. La membrane à électrolyte polymère présente une excellente stabilité de forme et présente une résistance améliorée aux radicaux qui apparaissent pendant le fonctionnement. Par conséquent, la membrane à électrolyte polymère présente une excellente stabilité vis-à-vis des radicaux (c'est-à-dire la stabilité chimique), présente d'excellentes performances de conductivité ionique, et peut réduire la perméabilité à l'hydrogène.
PCT/KR2018/011372 2017-09-29 2018-09-27 Membrane à électrolyte polymère, son procédé de fabrication et ensemble membrane-électrodes la comprenant Ceased WO2019066460A1 (fr)

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JP2020535951A JP6987996B2 (ja) 2017-09-29 2018-09-27 高分子電解質膜及びその製造方法並びにこれを含む膜−電極アセンブリー
CN201880063265.2A CN111164813A (zh) 2017-09-29 2018-09-27 聚合物电解质膜、其制备方法和包括所述聚合物电解质膜的膜电极组件
EP18863595.7A EP3691010A4 (fr) 2017-09-29 2018-09-27 Membrane à électrolyte polymère, son procédé de fabrication et ensemble membrane-électrodes la comprenant
US16/646,271 US11444305B2 (en) 2017-09-29 2018-09-27 Polymer electrolyte membrane, method for manufacturing same, and membrane electrode assembly comprising same

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US11791521B2 (en) * 2019-09-13 2023-10-17 Hutchinson Technology Incorporated Electrode tabs and methods of forming
CN118546413A (zh) * 2024-05-31 2024-08-27 苏州科润新材料股份有限公司 一种复合质子交换膜的后处理工艺

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JP2011508369A (ja) * 2007-12-14 2011-03-10 ゴア エンタープライズ ホールディングス，インコーポレイティド 高安定性燃料電池膜及びその製造方法
KR20140082378A (ko) * 2012-12-24 2014-07-02 뉴로엘리싯 주식회사 이차전지용 유무기 다공성분리막의 제조방법 및 이로부터 제조된 유무기 다공성분리막
KR101639536B1 (ko) * 2015-12-21 2016-07-13 한국에너지기술연구원 강화복합막 및 이의 제조방법

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JP2009094010A (ja) * 2007-10-11 2009-04-30 Samsung Sdi Co Ltd 燃料電池用電解質膜積層体、膜電極接合体、及び燃料電池用電解質膜積層体の製造方法
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KR20140082378A (ko) * 2012-12-24 2014-07-02 뉴로엘리싯 주식회사 이차전지용 유무기 다공성분리막의 제조방법 및 이로부터 제조된 유무기 다공성분리막
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11791521B2 (en) * 2019-09-13 2023-10-17 Hutchinson Technology Incorporated Electrode tabs and methods of forming
CN118546413A (zh) * 2024-05-31 2024-08-27 苏州科润新材料股份有限公司 一种复合质子交换膜的后处理工艺

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