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WO2019107996A1 - Membrane d'électrolyte polymère, son procédé de fabrication, et ensemble membrane-électrodes la comprenant - Google Patents

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

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Publication number
WO2019107996A1
WO2019107996A1 PCT/KR2018/015025 KR2018015025W WO2019107996A1 WO 2019107996 A1 WO2019107996 A1 WO 2019107996A1 KR 2018015025 W KR2018015025 W KR 2018015025W WO 2019107996 A1 WO2019107996 A1 WO 2019107996A1
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WIPO (PCT)
Prior art keywords
ion conductor
group
repeating unit
porous support
polymer electrolyte
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Ceased
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PCT/KR2018/015025
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English (en)
Korean (ko)
Inventor
이동훈
김나영
이은수
박중화
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Kolon Industries Inc
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Kolon Industries Inc
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Priority claimed from KR1020180150117A external-priority patent/KR102293177B1/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Priority to CN201880077251.6A priority Critical patent/CN111418104B/zh
Priority to JP2020527773A priority patent/JP6957754B2/ja
Priority to US16/766,957 priority patent/US11302949B2/en
Priority to EP18884648.9A priority patent/EP3719904B1/fr
Publication of WO2019107996A1 publication Critical patent/WO2019107996A1/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
    • 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
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • 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
    • 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 including the same, and more particularly, to a polymer electrolyte membrane having both excellent durability and ionic conductivity and capable of reducing hydrogen permeability, To a membrane electrode assembly comprising the membrane electrode assembly.
  • 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 pollutant emission, it is becoming 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 kind of the electrolyte.
  • PEMFC polymer electrolyte fuel cell
  • 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 fluorine-based polymer material which is generally used in fuel cells for transportation at present, has a weak resistance to radicals generated during operation and low stability to the radicals, that is, chemical stability.
  • the hydrogen ion conductivity is high, 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 both durability and ionic conductivity and can reduce hydrogen permeability.
  • Another object of the present invention is to provide a method for producing the polymer electrolyte membrane.
  • a fluorine-based support comprising a plurality of voids by the microstructure of a polymer fibril, and a fluorine-based support which is located on one or both sides of the fluorine-
  • a heterogeneous complex porous support comprising a nanoweb containing voids of the heterogeneous composite porous support, and an ion conductor filling the voids of the heterogeneous complex porous support.
  • the nano-web may be formed by electrospinning on one side or both sides of the fluorine-based support.
  • the fluorine-based support may have a thickness of 2 to 40 ⁇ , and the nano-web may have a thickness of 10 to 50 ⁇ .
  • the polymer electrolyte membrane is disposed on one surface of the heterogeneous complex porous support and includes a first ion conductor layer including a first ion conductor, a second ion conductor layer located on another surface of the heterogeneous complex porous support, And the heteropoly complex porous support comprising any one selected from the group consisting of the first ion conductor, the second ion conductor, and combinations thereof.
  • the heterogeneous complex porous support includes a first ion conductor that fills the gap on one side where the first ion conductor layer is located and a second ion conductor that fills the gap on the other surface where the second ion conductor layer is located, . ≪ / RTI >
  • 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 each independently selected from the group consisting of F, Cl and a fluorinated alkyl group having 1 to 10 carbon atoms, X is an ion exchange group, and a is 0 to 3 Real number, and 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.
  • a method for preparing a fluorine-containing polymer comprising the steps of preparing a fluorine-based support containing a plurality of voids by a microstructure of a polymer fibril, electrospinning on one or both sides of the fluorine- Forming a nano-web integrated in the form of a nonwoven fabric including voids to prepare a heterogeneous composite porous support, and filling the pores of the heterogeneous composite porous support with an ion conductor.
  • the step of filling the pores of the heterogeneous complex porous support with an ion conductor may include forming a first ion conductor layer including a first ion conductor on one surface of the heterogeneous complex porous support, And forming a second ion conductor layer including the second ion conductor layer.
  • a membrane-electrode assembly comprising an anode electrode and a cathode electrode facing each other, and the polymer electrolyte membrane 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 has both excellent durability and ion conductivity and can reduce hydrogen permeability.
  • FIG. 1 is a cross-sectional view schematically showing a polymer electrolyte membrane according to an embodiment of the present invention.
  • FIG. 2 is a schematic view of a nozzle type electrospinning device.
  • FIG. 3 is a schematic cross-sectional view of a membrane-electrode assembly according to an embodiment of the present invention.
  • FIG. 4 is a schematic diagram showing the overall configuration of a fuel cell according to an embodiment of the present invention.
  • 5 and 6 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 contained in the above general formula, But may also include repeating units represented by various types of chemical formulas.
  • the polymer electrolyte membrane according to an embodiment of the present invention includes a porous support including a plurality of pores, and an ion conductor filling the pores of the porous support.
  • the fluorine-based support including a plurality of voids by the microstructure of the polymeric fibrils may include a plurality of voids due to a fine structure composed of nodes connected to each other by fibrils,
  • the fluorine-based support may be an extended fluorine-based support.
  • the fluorine-based support may comprise a fluorinated polymer, preferably a perfluorinated polymer, which is highly resistant to thermal and chemical degradation.
  • the PTFE is commercially available and can be suitably used as the porous support and has a microstructure of a polymer fibril or a microstructure in which nodes are connected to each other by fibrils.
  • (e-PTFE) sheet can also be suitably used as the porous support, and PTFE having the fine structure of the polymer fibril free from the nodule can be suitably used as the porous support.
  • the e-PTFE sheet 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 fluorine-based support may be from 2 ⁇ to 40 ⁇ , preferably from 5 ⁇ to 20 ⁇ . If the thickness of the fluorine-based support is less than 2 ⁇ , the mechanical strength may be significantly reduced. On the other hand, if the thickness exceeds 40 ⁇ , the resistance loss may increase and the weight and integration may be reduced.
  • the nanoweb located on one side or both sides of the fluorine-based support may be a nanoweb integrated in the form of a nonwoven fabric in which the nanofibers include a plurality of voids.
  • the nanofibers exhibit excellent chemical resistance and can be preferably used because they are hydrophobic and have no fear of morphological change due to moisture in a high humidity environment.
  • the polymer include nylon, polyimide, polyaramid, polyetherimide, polyacrylonitrile, polyaniline, polyethylene oxide, polyethylene naphthalate, polybutylene terephthalate, styrene butadiene rubber, polystyrene, polyvinyl chloride, polyvinyl A hydrocarbon-based polymer such as an alcohol, polyvinylidene fluoride, polyvinyl butylene, polyurethane, polybenzoxazole, polybenzimidazole, polyamideimide, polyethylene terephthalate, polyphenylene sulfide, polyethylene, polypropylene; (Perfluoroacryl) vinyl ether co-polymer (PFA) or polytetrafluoroethylene (polyvinylidene difluoride), tetrafluoroethylene hex
  • the nano-web may have a basis weight of 5 g / m 2 to 30 g / m 2 . If the basis weight of the nano-web is less than 5 g / m 2 , visible pores may be formed and it may be difficult to function as a porous support. If the basis weight of the nano-web exceeds 30 g / m 2 , Shaped.
  • the thickness of the nano-web may be between 10 ⁇ m and 50 ⁇ m, and specifically between 15 ⁇ m and 43 ⁇ m. If the thickness of the nano-web is less than 10 ⁇ , the mechanical strength may be lowered. If the thickness of the nano-web is more than 50 ⁇ , the resistance loss may increase and the weight and integration may be decreased.
  • the porosity of the heterogeneous complex porous support may be 45% or more, and may be 60% or more.
  • the heterogeneous complex porous support preferably has a porosity of 90% or less. If the porosity of the heterogeneous composite porous support is more than 90%, the morphological stability may be deteriorated and 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 heterogeneous complex 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 (%) (volume of air in heterogeneous complex porous support / total volume of heterogeneous complex porous support) X 100
  • the heterogeneous complex porous support is a porous support comprising a mixture of the fluorine-based support and the nanomaterial of the nano-web.
  • the heterogeneous composite material may have mechanical strength and resistance reduction effects.
  • nano-web may be simply laminated on the fluorine-based support
  • the nano-web is formed by electrospinning directly on one or both sides of the fluorine-based support, have.
  • the polymer electrolyte membrane is a polymer electrolyte membrane in the form of a reinforced composite membrane in which an ion conductor is filled in the pores of the heterogeneous complex porous support.
  • the polymer electrolyte membrane may include a first ion conductor layer disposed on one surface of the heterogeneous complex porous support and a second ion conductor layer disposed on another surface of the heterogeneous complex porous support.
  • the first ion conductor layer and the second ion conductor layer may be formed in such a manner that the ion conductor remaining after filling the voids of the heterogeneous complex porous support forms a thin film on the surface of the heterogeneous complex porous support.
  • FIG. 1 is a cross-sectional view schematically showing an example of the polymer electrolyte membrane 150.
  • the polymer electrolyte membrane 150 includes a fluorine-based support 11 including a plurality of voids due to the microstructure of the polymeric fibrils, and a fluorine-based support 11 disposed on both sides of the fluorine- (10) comprising nanofibers (12) integrated into a nonwoven fabric comprising a plurality of voids.
  • the first ion conductor layer 21 is located on one side of the heterogeneous complex porous support 10 and the second ion conductor layer 31 is located on the other side of the heterogeneous complex porous support 10.
  • the first ion conductor layer 21 may comprise a first ion conductor 20 and the second ion conductor layer 31 may comprise a second ion conductor 30, 10 may include any one selected from the group consisting of the first ion conductor 20, the second ion conductor 30, and combinations thereof.
  • the present invention is not limited thereto, and the first ion conductor layer 21 and the second ion conductor layer 31 may include the same ion conductor, 10 may also be filled with one ionic conductor.
  • the first ion conductor 20 may include a combination of the first ion conductor 20 and the second ion conductor 30.
  • the first ion conductor 20 may include a combination of the first ion conductor 20 and the second ion conductor 30, 1 ion conductor layer 21 is positioned and the second ion conductor 30 is filled with the heteropolyporous porous body 10 in which the second ion conductor layer 30 is located, The pores of the other surface of the support body 10 may be filled.
  • the present invention is not limited to the above-described FIG. 1, and the pores of the heterogeneous complex porous support 10 may be filled with only the first ion conductor 20 or the second ion conductor 30.
  • 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 surface 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 surface of the porous support, The shape stability of the polymer electrolyte membrane can be ensured and the durability performance of the polymer electrolyte membrane can be ensured.
  • the thickness ratio of the first ion conductor layer may be 10% to 200%, particularly 50% to 100%, of the total thickness of the porous support, and the thickness ratio of the second ion conductor layer May be 10% to 200%, and more preferably 50% to 100%, of the total thickness of the porous support. 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 surface 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 pores of the porous support are filled with the first ion conductor, and on one surface of the porous support, 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 ketone, 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 sulf
  • 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 may be used as the anion conductor.
  • 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 are a fluorinated polymer including a fluorinated side chain.
  • the second ion conductor may have different lengths of the side chains.
  • fluorinated means that at least 90 mole% of the total number of halogen and hydrogen atoms is replaced by fluorine atoms.
  • the fluorinated polymer includes a polymer skeleton and cyclic side chains attached to the skeleton, and 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).
  • R f is independently any one selected from the group consisting of F, Cl, and fluorinated alkyl groups 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
  • n may be an integer of 1 to 10.
  • 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 an integer 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 an integer of 0 to 10, preferably 0 or an integer 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 an integer 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-.
  • the n 41 may be an integer of 0 to 10, preferably 0 or an integer 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 an integer 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 an integer of 0 to 10, preferably 0 or an integer 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 g / mol to 1,000,000 g / mol, and preferably have a weight average molecular weight of 100,000 g / mol to 500,000 g / mol. If the weight average molecular weight of the first ion conductor and the second ion conductor is less than 100,000 g / mol, 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 exceeds 500,000 g / mol, the solubility can be reduced.
  • the heterogeneous complex porous support is a polymer- Which is advantageous in terms of film stability.
  • the ion conductor is easily desorbed or discharged from the heterogeneous complex porous support, You may lose your sex.
  • 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 ionic conductor may have a degree of sulfonation of 1 mol% to 100 mol%, preferably 50 mol% 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 ion conductivity can be improved and the membrane resistance can be reduced.
  • the morphology stability of the polymer electrolyte membrane can be ensured by introducing the second ion conductor having a high molar ratio of the unit.
  • any one selected from the group consisting of the heterogeneous complex porous support, 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 layer.
  • the antioxidant capable of decomposing the peroxide or the radical By including 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 layer, The chemical durability of the film 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 the radical may be a transition metal capable of decomposing the peroxide or radical, a noble metal capable of decomposing the peroxide or radical, an ionic form thereof, a salt form thereof , Or an oxide thereof.
  • the transition metal capable of decomposing the peroxide or the radical may be at least one selected from the group consisting of Ce, Ni, W, Co, Cr, Zr, Y, And may be any one selected from the group consisting of Mn, Fe, Ti, V, Mo, La and Ne.
  • 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, ion, molybdenum ion, a lanthanum ion, neodymium ion, silver ion, a platinum ion, a ruthenium ion, a palladium ion, and may be any one selected from the group consisting of rhodium ion, for example the cerium in detail example cerium trivalent ions (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, 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 antioxidant capable of decomposing the peroxide or the radical is dispersed in the polymer electrolyte membrane or the catalyst electrode in order to prevent deterioration due to radicals of the polymer electrolyte membrane, the peroxide or the radical is decomposed during operation of the fuel cell There may be a problem that an antioxidant that can be dissolved is eluted.
  • it may include an organic second antioxidant capable of fixing the antioxidant.
  • the organic second antioxidant may be a compound containing a resonance structure based on a double bond of a carboxylic acid, a hydroxyl group and carbon.
  • the organic second antioxidant having such a structure has a molecular size effect that can not utilize a passage eluted as it has a larger molecular size than the ion clusters and channels in the polymer electrolyte membrane, The hydroxyl group and the polymer in the polymer electrolyte membrane can be prevented from being eluted through hydrogen bonding.
  • organic second antioxidant examples include syringic acid, vanillic acid, protocatechuic acid, coumaric acid, caffeic acid, ferulic acid, acid, chlorogenic acid, cynarine, galic acid, and mixtures thereof.
  • the second antioxidant may be included in an amount of 0 to 200 parts by weight based on 100 parts by weight of the first antioxidant, 30 parts by weight to 100 parts by weight.
  • the antioxidant is similar to the case of using only the first antioxidant. Therefore, when the content of the second antioxidant is more than 200 parts by weight, The uniformity of the inside of the polymer electrolyte membrane may be lowered.
  • a method of manufacturing a polymer electrolyte membrane comprising: preparing a fluorine-based support including a plurality of voids by a microstructure of a polymeric fibril; electrospinning the nanofibers on one or both surfaces of the fluorine- Forming a nanocomposite in the form of a nonwoven fabric including a plurality of voids to prepare a heterogeneous composite porous support, and filling the pores of the heterogeneous composite porous support with an ion conductor.
  • the PTFE powder produced by the dispersion polymerization is extruded into a rod-shaped paste in the presence of a lubricant such as solvent naphtha or white oil, and the rod-shaped paste extrusion
  • a lubricant such as solvent naphtha or white oil
  • the water (cake) is rolled to prepare a PTFE-free sheet.
  • the unfired sheet is stretched at an arbitrary ratio in the longitudinal direction (MD direction) and / or the width direction (TD direction).
  • the elongated PTFE sheet can be produced by removing the charged liquid lubricant during or after the elongation by heating or extraction.
  • the amorphous content of the PTFE may be increased by heat-treating the elongated PTFE (e-PTFE) at a temperature exceeding the melting point of the PTFE (about 342 ° C).
  • the nanofibers are electrospun on one side or both sides of the fluorine-based support to form a nano-web in which the nanofibers are integrated in the form of a nonwoven fabric including a plurality of voids to prepare a heterogeneous composite porous support.
  • the step of forming the nano-web includes the steps of preparing an electrospinning solution, and electrospinning the prepared electrospinning solution on one surface or both surfaces of the heterogeneous composite porous substrate.
  • the step of preparing the electrospinning solution is to prepare a solution containing a polymer for forming nanofibers through electrospinning.
  • the electrospinning solution may be a solution of a polymer used in the above- N-dimethylacetamide, N, Ndimethyl formamide, dimethylsulphoxide, N-methyl-2-pyrolidone, triethylphosphate, methyl
  • the prepared electrospinning solution is electrospun to produce a nano-web in which nanofibers are integrated into a nonwoven fabric including a plurality of pores.
  • the electrospinning may be performed using the electrospinning apparatus shown in FIG. 2 is a schematic view of a nozzle type electrospinning device. 2, the electrospinning is performed by using a metering pump 2 in a solution tank 1 in which the electrospinning solution is stored, a plurality of nozzles 3 to which high voltage is applied by the high voltage generator 6, The electrospinning solution is fed to the electrospinning solution by the difference in electric energy between the nozzle 3 or the tip of the electrospinning unit and the accumulation unit 4, that is, the voltage difference. The formed jet is whipped and stretched by the electric field to become thinner and the solvent is vaporized so that solid fibers are accumulated in the integrated portion 4. [
  • the nanofiber composing the nanofiber is polyimide
  • the nanofiber may be prepared by electrospinning a polyamic acid (PAA) to form a nanofiber precursor comprising the PAA nanofibers, followed by a subsequent heat treatment or chemical imaging Can be prepared through a hydrogenation reaction.
  • PAA polyamic acid
  • the pores of the heterogeneous complex porous support are filled with an ion conductor.
  • the step of filling the voids of the heterogeneous complex porous support with the ion conductor may be carried out by impregnating or impregnating the heterogeneous complex porous support in a solution containing the ion conductor.
  • the step of filling the pores of the heterogeneous complex porous support with an ion conductor includes the steps of: forming a first ion conductor layer including a first ion conductor on one surface of the heterogeneous complex porous support; 2 < / RTI > ionic conductor to form a second ion conductor layer.
  • the first ion conductor is filled in the pores of one surface of the heterogeneous complex porous support, and the first ion conductor remaining on the surface of the heterogeneous complex porous support is filled with a first ion conductor
  • the second ion conductor is filled in the pores of the other surface of the heterogeneously complex porous support, and the second ion conductor remaining on the other surface of the heterogeneous complex porous support is filled with the second ion conductor on the surface of the other surface of the heterogeneously complex porous support.
  • the pores of the heterogeneous complex porous support may be filled only with the first ion conductor, and after forming the first ion conductor layer, It is also possible to form only the second ion conductor layer on the other surface of the substrate.
  • the step of filling the voids of the heterogeneous complex porous support with the first ion conductor and the second ion conductor generally comprises the step of supporting or impregnating the heterogeneous complex porous support with a solution containing the first ion conductor or the second ion conductor .
  • the step of filling the voids of the heterogeneous composite porous support with the first ion conductor and the second ion conductor may be performed by a combination of bar coating, comma coating, slot die, screen printing, spray coating, doctor blade, laminating and combinations thereof Or by a method selected from the group.
  • the existing processes may be used as they are, except that the first ion conductor and the second ion conductor are filled on one surface and the other surface of the heterogeneous complex porous substrate, respectively.
  • the first ion conductor and the second ion conductor may be filled into the heterogeneous complex 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 only a part of the heterogeneous complex porous support.
  • the content of the antioxidant added to the solution or dispersion containing the first ion conductor or the second ion conductor can be controlled, The amount of the antioxidant to 100 parts by weight of the ion conductor can be controlled.
  • 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.
  • filling the pores of the heterogeneous complex 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 heterogeneous complex 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.
  • 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 to 30 minutes.
  • the temperature can not be higher than the melting point of the heterogeneous complex porous support.
  • the method for producing a polymer electrolyte membrane may further include the steps of: preparing a plurality of the heterogeneous complex porous supports comprising the first ion conductor and the second ion conductor; and laminating the plurality of heterogeneously complex porous supports .
  • the laminating method can be applied when the plurality of heterogeneous composite 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 heterogeneous composite 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 150 and the fuel cell electrodes 120 and 120 'disposed on both sides of the polymer electrolyte membrane 150 do.
  • an oxidation reaction is performed on one surface of the polymer electrolyte membrane 150 to generate hydrogen ions and electrons from the fuel passed through the electrode substrate 140 to the catalyst layer 130.
  • the electrode 120 causing the polymer electrolyte membrane 150 is referred to as an anode electrode and hydrogen ions supplied to the other surface of the polymer electrolyte membrane 150 through the polymer electrolyte membrane 150 pass through the electrode substrate 140 '
  • the electrode 120 'that generates a reducing reaction to generate water from the oxidant transferred to the cathode 130' is referred to as a cathode electrode.
  • the catalyst layers 130 and 130 'of the anode and cathode electrodes 120 and 120' 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% by weight to 80% by weight based on the total weight of the catalyst layers 130 and 130 '. If the amount is less than 20% by weight, , The agglomeration of the catalyst particles may cause the active area to be reduced and the catalytic activity to be lowered inversely.
  • the catalyst layers 130 and 130 ' may include a binder for enhancing adhesion of the catalyst layers 130 and 130' and for transferring hydrogen ions.
  • a binder for enhancing adhesion of the catalyst layers 130 and 130' 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 ionic 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 adhesion to the polymer electrolyte membrane 150. 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% by weight to 80% by weight based on the total weight of the catalyst layers 130 and 130 '. 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 substrate may be used as the electrode substrate 140 or 140 '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 140 or 140 ' is made of a fluorine-based resin that is water repellent to prevent the reactant diffusion efficiency from being lowered due to water generated when the fuel cell is driven.
  • fluorine-based resin examples include polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride alkoxyvinyl ether, fluorinated ethylene propylene ( Fluorinated ethylene propylene), polychlorotrifluoroethylene, or copolymers thereof.
  • the microporous layer may further include a microporous layer for enhancing the reactant diffusion effect in the electrode substrate 140 or 140 '.
  • 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 140, 140 '.
  • 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 150 according to the present invention is used as the polymer electrolyte membrane 150 have.
  • the fuel cell according to another embodiment of the present invention may include the membrane-electrode assembly 100 described above.
  • FIG. 4 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 210 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.
  • a PTFE porous support was prepared as a fluorinated polymer containing a plurality of pores by the microstructure of the polymer fibrils.
  • the electrospinning solution was electrospun on both sides of the PTFE porous support under the conditions of a voltage of 3 kV and a discharge rate of 1.5 ml / min using the electrospinning device of FIG. 2 to prepare a nanobubbelite precursor.
  • the nanocavity precursor thus prepared was heat-treated at 350 ° C to prepare a heterogeneous complex porous support (porosity: 40% by volume).
  • a PTFE porous support was prepared as a fluorinated polymer containing a plurality of pores by the microstructure of the polymer fibrils.
  • an electrospinning solution was prepared by dissolving PVdF in dimethylacetamide at a concentration of 18% (w / w).
  • the viscosity of the electrospinning solution was 3000 cP.
  • the electrospinning solution was electrospun on both sides of the PTFE porous support under the conditions of a voltage of 60 kV and a discharge rate of 20 cc / min using the electrospinning device of FIG. 2 to prepare a heterogeneous composite porous support.
  • Polyamic acid was dissolved in dimethylformamide to prepare 5 L of an electrospinning solution of 480 poise.
  • the prepared electrospinning solution was transferred to a solution tank, and the solution was supplied to a spinning chamber having 20 nozzles and a high voltage of 3 kV through a metering gear pump and spinning to prepare a nano-web precursor. At this time, the supply amount of the solution was 1.5 ml / min.
  • the prepared nanobeb precursor 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 nano-webs were prepared using electrospinning in the same manner as in Comparative Preparative Example 2-1, except that two nanowebs having a thickness of half the thickness of the nano-webs prepared in Comparative Preparation Example 2-1 were prepared, The two nanowebs were laminated to prepare a porous support.
  • Two PTFE porous supports having a thickness half the thickness of the PTFE porous support used in Production Example 2-2 were prepared, and then the two PTFE porous supports were laminated to prepare a porous support.
  • the molar ratio of the hydrophilic repeating unit: hydrophobic repeating unit molar ratio of 1: 3.5 prepared in Preparation Example 1-1 to the hydrophilic repeating unit: hydrophobic repeating unit prepared in Preparation Example 1-2 was 1: 2.5 Ion conductor was dissolved in DMAc in an amount of 20% by weight to prepare an ion conductor solution.
  • a polymer electrolyte membrane was prepared by impregnating the ion conductor solution prepared in Preparation Example 1-1 or Preparation Example 1-2 on one surface and the other surface of the heterogeneous complex porous substrate prepared in Preparation Example 2-1.
  • the impregnation method may be performed by first impregnating an ion conductor having a relatively high molar ratio of the hydrophilic repeating units prepared in Preparation Example 1-2 on one surface with respect to the heterogeneous complex porous support, A first ion conductor layer was formed on one surface of the heterogeneous complex porous support, and a second ion conductor layer was formed on the other surface of the heterogeneous complex porous support by using an ion conductor having a relatively high molar ratio of the hydrophobic repeating units prepared in Preparation Example 1-1 To fill the pores of the other surface of the heterogeneous complex porous support, and then a second ion conductor layer was formed on the surface of the other surface of the heterogeneous complex porous support.
  • 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 heterogeneous complex porous support and the thickness of the ion conductor layer formed on the surface of the heterogeneous complex porous support.
  • 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.
  • the ionic conductor solution prepared by dissolving the ionic conductor prepared in Preparation Example 1-1 at 20 wt% in DMAc was impregnated with the porous substrate prepared in Comparative Preparation Example 2-1 twice for 30 minutes, The mixture was allowed to stand under reduced pressure for 1 hour, and dried at 80 DEG C under vacuum for 10 hours to prepare a polymer electrolyte membrane. At this time, the weight of the ion conductor was 65 mg / cm 2 .
  • 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 Comparative Preparation Example 2-1 twice for 30 minutes, The mixture was allowed to stand under reduced pressure for 1 hour, and dried at 80 DEG C under vacuum for 10 hours to prepare a polymer electrolyte membrane. At this time, the weight of the ion conductor was 65 mg / cm 2 .
  • Example 1-1 The procedure of Example 1-1 was repeated except that the porous support prepared in Comparative Preparation Example 2-2 was used instead of the heterogeneously complex porous support prepared in Production Example 2-1. To prepare a polymer electrolyte membrane.
  • Example 1-1 The procedure of Example 1-1 was repeated except that the porous support prepared in Comparative Preparation Example 2-3 was used instead of the heterogeneously complex porous support prepared in Production Example 2-1. To prepare a polymer electrolyte membrane.
  • 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.
  • FIG. 5 shows AFM images of one surface impregnated with an ion conductor having a relatively high molar ratio of hydrophobic repeating units having a molar ratio of hydrophilic repeating units: hydrophobic repeating units of 1: 3.5 prepared in Preparation Example 1-1
  • FIG. 6 is an AFM image of one surface impregnated with an ion conductor having a relatively high molar ratio of hydrophilic repeating units having a molar ratio of hydrophilic repeating units: hydrophobic repeating units of 1: 2.5 prepared in Preparation Example 1-2 .
  • the morphology of the ionic conductors having different molar ratios of the hydrophilic repeating units: hydrophobic repeating units can be observed, and the hydrophilic repeating units of the ionic conductors: the moles of the hydrophobic repeating units It can be confirmed that the structure of the ion conductor can be controlled through the ratio control.
  • An ion conductor solution containing 30 wt% of a fluorinated polymer (3M company Dyneon) having an equivalent weight (EW) of 725 and a side chain length of 0 in the above formula (1) and b being 3 was dissolved in a first ion conductor solution
  • the polymer electrolyte membrane was prepared by impregnating the ion conductor solution on one surface and the other surface of the heterogeneous complex porous support prepared in Preparation Example 2-2.
  • An ion conductor solution (Chemers, product of Nafion solution) containing 5 wt% of fluorinated polymer having an equivalent weight (EW) of 1100 and a side chain length of 1 in the above formula (1) and b being 2 was prepared .
  • a PTFE porous support was impregnated with the ion conductor solution as a fluorinated polymer containing a plurality of voids by the microstructure of the polymer fibrils to prepare a polymer electrolyte membrane.
  • 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 Example 1-1 1: 2.5 + 1: 3.5 1) 22-23 1128 97 Nafion211 commercial membrane - 25 1184 89
  • the thickness ratio is a sum of the thickness impregnated into the heterogeneous complex porous support and the thickness of the ion conductor layer formed on the surface of the heterogeneous complex porous support.
  • the polymer electrolyte membrane prepared in the above example includes two kinds of ion conductors, which are fluorinated polymers having different lengths of the side chains. Therefore, in the comparative example including only one ion conductor The cell performance and the open circuit voltage retention ratio are relatively higher than those of the prepared polymer electrolyte membrane.
  • Example 1-1 The polymer electrolyte membranes prepared in Example 1-1, Comparative Example 1-3, and Comparative Example 1-4 were measured for dimensional change and hydrogen permeability, and the results are shown in Table 4 below.
  • the dimensional change rate (shrinkage ratio) was obtained by immersing the sample in water at 100 ° C for 10 minutes, taking out the sample, leaving it at room temperature for 30 minutes, and measuring the shrinkage in the longitudinal direction before and after immersion.
  • the hydrogen permeability of the sample was measured using a membrane-electrode assembly, and hydrogen and nitrogen, which had passed through a humidifier, were supplied to both electrodes, and the current density corresponding to the slope measured at a temperature of 65 ° C and a relative humidity of 100% .
  • Example 1-1 Nano Web + e-PTFE + Nano Web 20 ⁇ 23 3 or less 1.6 Comparative Example 1-3 Nano Web + Nano Web 20 ⁇ 23 1 or less 2.8 Comparative Example 1-4 e-PTFE + e-PTFE 20 ⁇ 23 15 1.5
  • the polymer electrolyte membrane prepared in Comparative Example 1-3 includes a porous support in which the nano-web is formed by laminating two layers of the porous support, the degree of dimensional change is small but the hydrogen permeability is very large. It can be seen that the polymer electrolyte membrane prepared in Example 1-4 contains a porous support in which the fluorine-based support is laminated in two layers, and the hydrogen permeability is small but the dimensional change rate is very large.
  • the polymer electrolyte membrane prepared in Example 1-1 includes the porous support in which the fluorine-based support and the nano-web are mixed, thereby reducing the hydrogen permeability while reducing the dimensional change rate .
  • Second discharge pipe 240 Oxidizing agent supply part
  • the present invention relates to a polymer electrolyte membrane, a method for producing the same, and a membrane electrode assembly including the same, wherein the polymer electrolyte membrane has both excellent durability and ion conductivity and can reduce hydrogen permeability.

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Abstract

La présente invention porte sur une membrane d'électrolyte polymère, son procédé de fabrication, et un ensemble membrane-électrodes la comprenant. La membrane d'électrolyte polymère comprend : un support à base de fluor contenant une pluralité de pores en raison de structures microfibrillaires polymères ; un support poreux hybride placé sur un côté ou des deux côtés du support à base de fluor et comprenant des nanotoiles obtenues en intégrant des nanofibres dans un tissu non tissé contenant une pluralité de pores ; et des conducteurs d'ions avec lesquels les pores du support poreux sont remplis. La membrane électrolyte polymère peut réduire la perméabilité à l'hydrogène tout en présentant une longévité et une conductivité d'ions excellentes.
PCT/KR2018/015025 2017-11-30 2018-11-30 Membrane d'électrolyte polymère, son procédé de fabrication, et ensemble membrane-électrodes la comprenant Ceased WO2019107996A1 (fr)

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CN201880077251.6A CN111418104B (zh) 2017-11-30 2018-11-30 聚合物电解质膜、其制备方法和包括其的膜电极组件
JP2020527773A JP6957754B2 (ja) 2017-11-30 2018-11-30 高分子電解質膜、その製造方法及びこれを含む膜電極アセンブリー
US16/766,957 US11302949B2 (en) 2017-11-30 2018-11-30 Polymer electrolyte membrane, method for manufacturing same, and membrane electrode assembly comprising same
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