WO2014178620A1 - 고분자 전해질막, 고분자 전해질막을 포함하는 막전극 접합체 및 막 전극 접합체를 포함하는 연료전지 - Google Patents
고분자 전해질막, 고분자 전해질막을 포함하는 막전극 접합체 및 막 전극 접합체를 포함하는 연료전지 Download PDFInfo
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- H—ELECTRICITY
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- 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]
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- 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
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- 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
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- 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
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- 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
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
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- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
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- H01M2300/0065—Solid electrolytes
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- 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
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Definitions
- the present specification provides a fuel cell including a polymer electrolyte membrane, a membrane electrode assembly including a polymer electrolyte membrane, and a membrane electrode assembly.
- a fuel cell is a high-efficiency power generation device, which has a higher efficiency than a conventional internal combustion engine, thus consumes less fuel and has the advantage of being a pollution-free energy source that does not generate environmental pollutants such as SO x , NO x , and VOC.
- SO x sulfur dioxide
- NO x nitrogen oxide
- VOC pollution-free energy source
- fuel cells have a variety of applications ranging from mobile power supplies for portable devices, transport power supplies for automobiles, and the like to distributed generation available for home and power projects.
- the potential market size is expected to be wide.
- AFC alkaline fuel cells
- PAFC phosphoric acid fuel cells
- MCFC molten carbonate fuel cells
- SOFC solid oxide fuel cells
- PEMFC Polymer electrolyte fuel cells
- DMFC direct methanol fuel cells
- gas diffusion electrode layers are disposed on both sides of the polymer electrolyte membrane, an anode is directed at the anode, and a cathode is directed at the anode, and water is generated by a chemical reaction through the polymer electrolyte membrane.
- the basic principle is to convert the reaction energy generated by this into electrical energy.
- ion conductive polymer electrolyte membrane is Nafion, a perfluorinated hydrogen ion exchange membrane developed by DuPont in the early 1960's.
- Nafion as a similar perfluorine-based polymer electrolyte commercial membrane, Asahi Chemicals' Aciplex-S membrane, Dow Chemical's Dow membrane, Asahi Glass Glass's Flemion film.
- the polymer electrolyte membrane has a thickness change and a volume change of 15 to 30% depending on the temperature and the degree of hydration, and thus the electrolyte membrane repeats swelling and shrinking depending on the fuel cell operating conditions. Or cracking will occur.
- hydrogen peroxide (H 2 O 2 ) or peroxide radicals are generated by reduction of oxygen at the cathode, which may degrade the electrolyte membrane.
- Polymer electrolyte membranes for fuel cells have been developed in the direction of improving mechanical and chemical durability in consideration of such phenomena that may occur during fuel cell operation.
- a porous support is used to impart mechanical properties and dimensional stability. Since the porous support must maintain mechanical durability without sacrificing performance, it is necessary to select a support of a suitable material having high porosity and excellent mechanical properties. In addition, since the ion conductivity of the membrane may vary greatly depending on the method of impregnating the ion conductor with the support and the type of the ion conductor, it is required to develop an ion conductor suitable for an effective method of impregnating the ion conductor and the reinforced composite electrolyte membrane.
- An object of the present specification is to provide a polymer electrolyte membrane. Furthermore, the present invention provides a membrane electrode assembly including the polymer electrolyte membrane and a fuel cell including the same.
- An exemplary embodiment of the present specification includes a mixed layer including an ion migration region and a support of a three-dimensional network structure, wherein the ion migration region has a structure in which two or more cells including a hydrocarbon-based ion conductive material are in three-dimensional contact with each other.
- a polymer electrolyte membrane having a limit of RH cycles of at least 20,000 times is provided.
- An exemplary embodiment of the present specification includes a mixed layer including an ion migration region and a support of a three-dimensional network structure, wherein the ion migration region has a structure in which two or more cells including a hydrocarbon-based ion conductive material are in three-dimensional contact with each other.
- the polymer electrolyte membrane provides a polymer electrolyte membrane having a maximum stress in the machine direction (MD) of 200 kgf / cm 2 or more.
- An exemplary embodiment of the present specification includes a mixed layer including an ion migration region and a support of a three-dimensional network structure, wherein the ion migration region has a structure in which two or more cells including a hydrocarbon-based ion conductive material are in three-dimensional contact with each other.
- the polymer electrolyte membrane provides a polymer electrolyte membrane having a maximum stress of 200 kgf / cm 2 or more in a vertical direction of a machine direction (MD) of the polymer electrolyte membrane.
- An exemplary embodiment of the present specification provides a membrane electrode assembly including the polymer electrolyte membrane.
- An exemplary embodiment of the present specification provides a fuel cell including the membrane electrode assembly.
- the polymer electrolyte membrane according to one embodiment of the present specification has an advantage of excellent durability. Specifically, when the membrane electrode assembly including the polymer electrolyte membrane according to one embodiment of the present specification is applied to a fuel cell, it may contribute to the performance improvement of the fuel cell. That is, the polymer electrolyte membrane according to one embodiment of the present specification may minimize deterioration of fuel cell performance in a fuel cell operating environment in which high temperature humidification and drying are repeated and shrinkage and expansion of the polymer electrolyte membrane are repeated, and constant performance may be maintained. To be.
- 1 and 2 illustrate one region of the surface of the polymer electrolyte membrane according to one embodiment of the present specification.
- FIG 3 illustrates one region of a cross section of the polymer electrolyte membrane according to one embodiment of the present specification.
- FIG. 4 illustrates a structure of a fuel cell according to an exemplary embodiment of the present specification.
- Figure 5 shows the results of measuring the maximum diameter of the surface cells of the polymer electrolyte membrane according to one embodiment of the present specification.
- Figure 7 shows the voltage according to the current density of the membrane electrode assembly prepared according to Experimental Example 2.
- An exemplary embodiment of the present specification includes a mixed layer including an ion migration region and a support of a three-dimensional network structure, wherein the ion migration region has a structure in which two or more cells including a hydrocarbon-based ion conductive material are in three-dimensional contact with each other.
- a polymer electrolyte membrane having a limit of RH cycles of at least 20,000 times is provided.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 40,000 times.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 50,000 times.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 60,000 times.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 70,000 times.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 75,000 times.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 80,000 times.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 100,000 times.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 120,000 times.
- the polymer electrolyte membrane may have a limit of RH cycles of at least 150,000 times.
- the polymer electrolyte membrane hardly causes a decrease in performance even in the number of RH cycles in the above range.
- the polymer electrolyte membrane may have a limit of RH cycles of 300,000 times or less.
- the polymer electrolyte membrane may have a limit of RH cycles of 500,000 times or less.
- the polymer electrolyte membrane according to one embodiment of the present specification has an advantage of excellent durability. Specifically, the polymer electrolyte membrane can be confirmed excellent durability through the RH cycle. More specifically, the polymer electrolyte membrane according to one embodiment of the present specification has an advantage that the durability decreases due to the volume change occurring during the execution of the RH cycle similar to the driving state of the fuel cell.
- the RH cycle of the present specification means that the polymer electrolyte membrane is made of MEA (membrane electrode assembly) and then the durability is measured in a fuel cell state.
- MEA membrane electrode assembly
- nitrogen is injected into the anode at a flow rate of 0.95 slm (standard liter per minute) at 80 ° C.
- nitrogen is injected into the cathode at a flow rate of 1.0 slm
- RH relative humidity
- the limit value of the RH cycle means the number of cycles until the damage occurs such that the polymer electrolyte membrane cannot be used as the MEA by performing the RH cycle.
- LSV linear sweep volta-mmetry
- the LSV injects hydrogen into the anode at a flow rate of 0.2 slm, injects nitrogen into the cathode at a flow rate of 0.2 slm, and measures the crossover of hydrogen at 0.1 to 0.4 V (2 mV / s). It means. That is, when the crossover value of hydrogen rises during the RH cycle, the polymer electrolyte membrane may be damaged. The degree of damage of the polymer electrolyte membrane may be determined according to the degree of increase of the crossover value of hydrogen. When the hydrogen crossover value rises sharply during the RH cycle, the polymer electrolyte membrane is damaged such that it does not perform properly, and the number of RH cycles at this time may be a limit of the RH cycle.
- the limit value of the RH cycle means the number of RH cycles in which the crossover value of hydrogen of the polymer electrolyte membrane capable of normal operation increases by five times or more.
- the polymer electrolyte membrane according to the exemplary embodiment of the present specification may maintain a constant performance with almost no performance degradation even when the limit value of the RH cycle is 20,000 or more.
- the maximum stress in the machine direction (MD) of the polymer electrolyte membrane may be 200 kgf / cm 2 or more.
- the maximum stress in the vertical direction of the machine direction (MD) of the polymer electrolyte membrane may be 200 kgf / cm 2 or more.
- An exemplary embodiment of the present specification includes a mixed layer including an ion migration region and a support of a three-dimensional network structure, wherein the ion migration region has a structure in which two or more cells including a hydrocarbon-based ion conductive material are in three-dimensional contact with each other.
- the polymer electrolyte membrane provides a polymer electrolyte membrane having a maximum stress in the machine direction (MD) of 200 kgf / cm 2 or more.
- An exemplary embodiment of the present specification includes a mixed layer including an ion migration region and a support of a three-dimensional network structure, wherein the ion migration region has a structure in which two or more cells including a hydrocarbon-based ion conductive material are in three-dimensional contact with each other.
- a polymer electrolyte membrane having a maximum stress in the vertical direction of the machine direction (MD) of the polymer electrolyte membrane is 200 kgf / cm 2 or more.
- the polymer electrolyte membrane may have a direction.
- the support may be prepared through uniaxial stretching or biaxial stretching of a polymer, and the orientation of the support by the stretching may determine the orientation of the polymer electrolyte membrane. Therefore, the polymer electrolyte membrane according to an exemplary embodiment of the present specification may have a directionality in a machine direction (MD) and a vertical direction of the machine direction (MD), and the polymer electrolyte membrane may have a stress and Physical properties, such as elongation, may show a difference.
- MD machine direction
- MD vertical direction of the machine direction
- the machine direction may be used as commonly used in the art. Specifically, the direction of the machine may mean the direction of the winding when manufactured in the form of a roll.
- the maximum stress in the machine direction (MD) of the polymer electrolyte membrane may be 300 kgf / cm 2 or more.
- the maximum stress in the machine direction (MD) of the polymer electrolyte membrane may be 500 kgf / cm 2 or more.
- the maximum stress in the machine direction (MD) of the polymer electrolyte membrane may be 800 kgf / cm 2 or more.
- the maximum stress in the machine direction (MD) of the polymer electrolyte membrane may be 900 kgf / cm 2 or more.
- the maximum stress in the vertical direction of the machine direction (MD) of the polymer electrolyte membrane may be 300 kgf / cm 2 or more.
- the maximum stress in the vertical direction of the machine direction (MD) of the polymer electrolyte membrane may be 400 kgf / cm 2 or more.
- the maximum stress in the vertical direction of the machine direction (MD) of the polymer electrolyte membrane may be 600 kgf / cm 2 or more.
- the maximum stress in the vertical direction of the machine direction (MD) of the polymer electrolyte membrane may be 800 kgf / cm 2 or more.
- the maximum elongation in the machine direction (MD) of the polymer electrolyte membrane may be 20% or more.
- the maximum elongation in the machine direction (MD) of the polymer electrolyte membrane may be 50% or more.
- the maximum elongation in the machine direction (MD) of the polymer electrolyte membrane may be 60% or more.
- the maximum elongation in the vertical direction of the machine direction (MD) of the polymer electrolyte membrane may be 10% or more.
- the maximum elongation in the vertical direction of the machine direction (MD) of the polymer electrolyte membrane may be 30% or more.
- the maximum stress of the present specification refers to the magnitude of the force per unit area at the moment of tearing of the polymer electrolyte membrane at 100 mm and the tensile velocity of 10 mm / min at 20 ° C. and 22% humidity. .
- the maximum elongation of the present specification is the increase rate of the polymer electrolyte membrane at the moment when the polymer electrolyte membrane is torn with a grip interval of 100 mm and a tensile velocity of 10 mm / min at 20 °C temperature and 22% humidity conditions. it means.
- the maximum stress and the maximum elongation of the present specification is measured by measuring a dogbone type polymer electrolyte membrane cut in accordance with the American Society for Testing and Materials (ASTM) standard at a speed of 10 mm / min with a united test machine (UTM). Means that.
- the UTM is a device for simultaneously measuring tensile strength and elongation, and is generally used in the art.
- the polymer electrolyte according to the exemplary embodiment of the present specification has a high maximum stress, there is an advantage that the polymer electrolyte may perform a function without changing performance for a long time in a fuel cell in which expansion and contraction of the electrolyte membrane are repeated by repeated high temperature humidification and drying. .
- the hydrocarbon-based material is a polymer having one or more cation exchange groups in the side chain, the ratio of the number of carbon atoms and the number of fluorine atoms contained in the polymer is 1: 0 or more and less than 1: 1,
- the cation exchange group may include one or more selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof.
- the hydrocarbon-based material may not include fluorine in the main chain or the side chain.
- the hydrocarbon-based material may have a ratio of the number of carbon atoms and the number of fluorine atoms included in the polymer may be 1: 0 or more and 2: 1 or less.
- the ion conductive material may include a cationic conductive material and / or an anionic conductive material.
- the ion conductive material may include a proton conductive material.
- the ion conductive material is a sulfonated benzimidazole-based polymer, sulfonated polyimide-based polymer, sulfonated polyetherimide-based polymer, sulfonated polyphenylene sulfide-based polymer, sulfonated polysul A group consisting of a von polymer, a sulfonated polyether sulfone polymer, a sulfonated polyether ketone polymer, a sulfonated polyether ether ketone polymer, a sulfonated polyphenylquinoxaline polymer, and a sulfonated partial fluorine polymer It may include one or two or more selected from.
- the sulfonated partial fluorine-based polymer is a sulfone group is bonded to at least one side chain, the ratio of the number of carbon atoms and fluorine atoms contained in the polymer is 1: 1: more than 1: 1. It may be a polymer that is less than one.
- the ion conductive material may have an ion conductivity of 1 mS / cm or more at 60 ° C. or more.
- an ion exchange capacity (IEC) of the ion conductive material may be 1 meq / g or more.
- the support may include a hydrocarbon-based material.
- the support may be a hydrocarbon-based support.
- the support may include a semi-crystalline polymer.
- the semi-crystalline polymer of the present specification may have a crystallinity of 20% to 80%.
- the semi-crystalline polymer may include polyolefin, polyamide, polyester, polyacetal (or polyoxymethylene), polysulfide, polyvinyl alcohol, copolymers thereof, and combinations thereof. It is not limited thereto.
- the support may include one derived from a polyolefin-based material.
- the polyolefin may include polyethylene (LDPE, LLDPE, HDPE, UHMWPE), polypropylene, polybutene, polymethylpentene, copolymers thereof and blends thereof.
- the polyamide may include, but is not limited to, polyamide 6, polyamide 6/6, nilo 10/10, polyphthalamide (PPA), copolymers thereof, and blends thereof.
- the polyester is polyester terephthalate (PET), polybutylene terephthalate (PBT), poly-1-4-cyclohexylenedimethylene terephthalate (PCT), polyethylene naphthalate (PEN) and liquid crystal polymer (LCP) ), but is not limited thereto.
- PET polyester terephthalate
- PBT polybutylene terephthalate
- PCT poly-1-4-cyclohexylenedimethylene terephthalate
- PEN polyethylene naphthalate
- LCP liquid crystal polymer
- Such polysulfides include, but are not limited to, polyphenylsulfides, polyethylene sulfides, copolymers thereof and blends thereof.
- the polyvinyl alcohols include, but are not limited to, ethylene-vinyl alcohols, copolymers thereof, and blends thereof.
- the polymer electrolyte membrane according to one embodiment of the present specification may include cells of uniform size.
- an average of the maximum diameter of the cell may be 0.25 ⁇ m or more and 0.4 ⁇ m or less.
- the standard deviation of the maximum diameter of the cell may be 0.05 ⁇ m or more and 0.2 ⁇ m or less.
- Figure 5 shows the results of measuring the maximum diameter of the surface cells of the polymer electrolyte membrane according to one embodiment of the present specification. Specifically, Figure 5 shows the maximum diameter of each cell located on the surface of the polymer electrolyte membrane according to one embodiment of the present specification, it is measured to show the frequency of the maximum diameter of each cell. Therefore, it can be seen that the polymer electrolyte membrane according to one embodiment of the present specification includes cells of uniform size.
- the cell in any plane parallel to the upper surface of the polymer electrolyte membrane, the cell is in one direction (x-axis direction) and the direction perpendicular thereto (y-axis direction) and the thickness direction of the polymer electrolyte membrane (z Two or more layers in the axial direction).
- the support may be a sponge structure in which two or more of the cells are distributed.
- the polymer electrolyte membrane may include a cross section of two or more cells in both a vertical cross section and a horizontal cross section.
- the diameter of the cross section of the cell herein may mean the length of the longest line across the cross section of the cell.
- the cross section of the cell on the horizontal surface of the polymer electrolyte membrane may have an aspect ratio of 1: 1 to 5: 1.
- the cross section of the cell on the vertical surface of the polymer electrolyte membrane may have an aspect ratio of 1: 1 to 10: 1.
- the diameter size of the cross section of the cell on the horizontal surface of the polymer electrolyte membrane may be 40 nm or more and 1,000 nm or less.
- the diameter size of the cross section of the cell on the vertical surface of the polymer electrolyte membrane may be 40 nm or more and 1,000 nm or less.
- the ratio of the number of cells per 100 ⁇ m 2 of the horizontal surface and the vertical surface of the polymer electrolyte membrane may be 1: 1 to 1: 5.
- the deviation of the number of cells of the vertical cross section and the horizontal cross section per 100 ⁇ m 2 of the polymer electrolyte membrane may be 0 or more and 500 or less.
- the average size of the diameter of the cross section of the cell may be 40 nm or more and 500 nm or less.
- the standard deviation of the diameter of the cross section of the cell may be 50 nm to 200 nm.
- the diameter of the cell may be 40 nm or more and 1000 nm or less.
- the support is composed of two or more nodes, and each node may include three or more branches.
- the distance between any one node of the support and another node adjacent to the support may be 10 nm to 500 nm.
- the length from the center of the cell to any point of the support may be 20 nm to 500 nm.
- the mixed layer may include 10 or more and 400 or less cells in any 1 ⁇ m 3 region.
- the mixed layer may include 10 to 150 cells in any 1 ⁇ m 3 region.
- the mixed layer may include 40 or more and 150 or less cells in any 1 ⁇ m 3 region.
- the ion migration region may be 40% by volume or more and 85% by volume or less with respect to the total volume of the mixed layer.
- the ion migration region may be 40% by volume or more and 80% by volume or less with respect to the total volume of the mixed layer.
- the ion migration region may be 40% by volume or more and 70% by volume or less with respect to the total volume of the mixed layer.
- the ion migration region may be 40 vol% or more and 60 vol% or less with respect to the total volume of the mixed layer.
- the ion migration region may be 40 vol% or more and 55 vol% or less with respect to the total volume of the mixed layer.
- the ion migration region may be 45 vol% or more and 65 vol% or less with respect to the total volume of the mixed layer.
- the ion migration region may be 45 vol% or more and 60 vol% or less with respect to the total volume of the mixed layer.
- the ion migration region of the present specification may mean a region excluding a skeleton formed by the support.
- the ion migration region may be a pore region when only the support is present.
- the ion conductive material may be included in the ion migration region, so that ions may move through the ion conductive material.
- the polymer electrolyte membrane when the ion conductive material is included in the range within the ion migration region, the polymer electrolyte membrane may exhibit excellent ion conductivity.
- the ion migration region of the polymer electrolyte membrane according to the present disclosure is 40% by volume or more and 85% by volume or less, it is possible to secure durability of the polymer electrolyte membrane and to ensure sufficient ion conductivity.
- the ion migration region is less than 40% by volume, the durability of the polymer electrolyte membrane is increased, but it is difficult to secure sufficient ion conductivity.
- the ion migration region exceeds 85% by volume, the ion conductivity of the polymer electrolyte membrane is increased, but it is difficult to secure durability.
- FIG. 1 and 2 illustrate one region of the surface of the polymer electrolyte membrane according to one embodiment of the present specification. Specifically, FIG. 1 illustrates one region of the horizontal surface of the polymer electrolyte membrane of the present specification, and FIG. 2 illustrates one region of the vertical surface of the polymer electrolyte membrane of the present specification. Furthermore, the region indicated by the dark region means the support, and the bright region means the ion migration region.
- the vertical surface may mean a surface in the thickness direction of the polymer electrolyte membrane.
- the horizontal surface is a surface perpendicular to the thickness direction of the polymer electrolyte membrane, and may mean a surface occupying a relatively large area.
- the ion migration region may mean a cross section of a cell, and a cell three-dimensionally contacting the illustrated cell exists inside the polymer electrolyte membrane.
- the cell of the present disclosure may have a spherical or spherical shape, a polyhedron, and when the cell is spherical, the cross section of the cell may have a closed shape with an aspect ratio of 1: 1 to 5: 1.
- the cell of the present specification may mean a virtual three-dimensional closed space surrounded by a virtual plane to be formed when the fibrous branches connecting the nodes and the nodes of the support are connected.
- the node may mean a site where two or more fibrous branches meet each other.
- the node may mean a site where two or more fibrous branches meet each other to form a branching point including three or more branches.
- FIG. 3 illustrates one region of a cross section of the polymer electrolyte membrane according to one embodiment of the present specification.
- the dotted line region of FIG. 3 is a virtual line, for partitioning the virtual three-dimensional closed space. Marked with dark areas are fibrous branches or nodes of the support, which are connected three-dimensionally.
- the cell of the present specification is a unit space of an ion migration region including an ion conductive material surrounded by fibrous branches of a support, and horizontal and vertical cross-sections of an imaginary three-dimensional closed space when surrounded by fibers of the support. It may be in the form of a circular or elliptical or single closed curve figure.
- the cell of the present specification means a volume having a predetermined size or more, and the diameter of the cell is less than 40 nm may not correspond to the cell.
- the diameter of the cell of the present specification may mean the length of the longest line across the cell.
- the ratio of the thickness of the mixed layer to the total thickness of the polymer electrolyte membrane provides a polymer electrolyte membrane that is 30% or more and 100% or less.
- the ratio of the thickness of the mixed layer to the total thickness of the polymer electrolyte membrane may be 50% or more and 100% or less.
- the ratio of the thickness of the mixed layer to the total thickness of the polymer electrolyte membrane may be 65% or more and 95% or less.
- the thickness ratio of the mixed layer with respect to the total thickness of the polymer electrolyte membrane is out of the range and less than 50% with respect to the total thickness of the polymer electrolyte membrane, the effect of increasing durability by the support of the mixed layer may be insignificant.
- the thickness of the mixed layer is less than 50% of the total thickness of the polymer electrolyte membrane, the polymer electrolyte membrane may be subject to the behavior of the pure layer made of an ion conductive material, which may lower durability.
- the polymer electrolyte membrane may be made of only the mixed layer.
- the ratio of the thickness of the mixed layer to the total thickness of the polymer electrolyte membrane may be 100%.
- the ratio of the thickness of the mixed layer to the total thickness of the polymer electrolyte membrane may be 50% or more and less than 100%.
- the polymer electrolyte membrane may further include a pure layer made of the ion conductive material on the upper and / or lower surfaces of the mixed layer.
- the bonding force between the polymer electrolyte membrane and the electrode may be lowered, which may cause a problem in which the separation phenomenon between the electrode and the polymer electrolyte membrane may occur during driving of the fuel cell.
- the thickness of the mixed layer provides a polymer electrolyte membrane, characterized in that 1 ⁇ m or more and 30 ⁇ m or less.
- the thickness of the mixed layer may be 1 ⁇ m or more and 25 ⁇ m or less.
- the thickness of the mixed layer may be 1 ⁇ m or more and 15 ⁇ m or less.
- the thickness of the mixed layer may be 5 ⁇ m or more and 15 ⁇ m or less.
- the thickness of the mixed layer according to the present disclosure is 1 ⁇ m or more and 30 ⁇ m or less, high ion conductivity and durability may be realized.
- the mixed layer is within the thickness range, a decrease in durability due to thickness reduction may hardly occur. That is, when the thickness of the mixed layer is less than 1 ⁇ m has a disadvantage that the durability is not maintained, when the thickness is more than 30 ⁇ m has a disadvantage that the ion conductivity may be lowered.
- the polymer electrolyte membrane may be made of only the mixed layer.
- the polymer electrolyte membrane may further include a pure layer including only the ion conductive material provided on the upper or lower surface of the mixed layer, or the upper and lower surfaces.
- the mixed layer may be formed by impregnating the support with an ion conductive material.
- a polymer electrolyte membrane without a pure layer when the ion conductive material is included to the support thickness range, a polymer electrolyte membrane without a pure layer may be formed.
- a polymer electrolyte membrane having a pure layer when the ion conductive material is included to exceed the thickness range of the support, a polymer electrolyte membrane having a pure layer may be prepared on the upper and / or lower surfaces of the mixed layer.
- the ion conductive material included in the mixed layer and the ion conductive material included in the pure layer may be different from each other.
- an ion conductive material of a different physical property from the ion conductive material included in the mixed layer is applied to the upper and / or lower surfaces of the mixed layer to form a pure layer. Can be.
- the pure layers provided on any one surface of the mixed layer may be independently stacked on two or more layers, and each layer may include a different ion conductive material from each other.
- the thickness of the pure layer provided on one side of the mixed layer may be each independently greater than 0 ⁇ m 6 ⁇ m or less.
- the pure layer may be provided on the upper and lower surfaces of the mixed layer, respectively.
- the thickness difference between the pure layers provided on the upper and lower surfaces of the mixed layer may be 50% or less of the thickness of the mixed layer. Specifically, the thickness difference between the pure layer provided on the upper and lower surfaces of the mixed layer may be 30% or less of the thickness of the mixed layer. According to one embodiment of the present specification, when the thickness difference between the pure layers is 0% of the thickness of the mixed layer, it means that the thicknesses of the pure layers provided on the upper and lower surfaces of the mixed layer are the same.
- the polymer electrolyte membrane when the thickness difference between the pure layer provided on the upper surface of the mixed layer and the pure layer provided on the lower surface of the mixed layer is 50% or less of the mixed layer thickness, the polymer electrolyte membrane may be repeatedly humidified and dried. Shrinkage and expansion of the upper and lower surfaces of the polymer electrolyte membrane are similar to prevent cracks from occurring.
- the thickness ratio of the mixed layer and the entire pure layer may be 1: 0 to 1: 4. Specifically, the thickness ratio of the mixed layer and the entire pure layer may be 1: 0 to 1: 1.5. More specifically, the thickness ratio of the mixed layer and the entire pure layer may be 1: 0 to 1: 1.
- the thickness ratio of the mixed layer to the pure layer is higher, high durability may be exhibited under conditions in which humidification and drying conditions are repeated.
- the total thickness of the polymer electrolyte membrane may be 3 ⁇ m or more and 36 ⁇ m or less.
- the ion migration region may include 60 vol% or more and 100 vol% or less of the ion conductive material.
- the ion migration region may include 70% by volume or more and 100% by volume or less of the ion conductive material.
- the air permeability of the polymer electrolyte membrane may be 1 hour / 100 ml or more.
- the polymer electrolyte membrane according to one embodiment of the present specification may form a dense structure to exhibit excellent performance in a fuel cell.
- the dense structure of the polymer electrolyte membrane may be known through the air permeability value.
- the polymer electrolyte membrane according to one embodiment of the present specification has an air permeability in the above range, it is possible to exhibit excellent performance of the electrolyte membrane in the fuel cell.
- the present specification provides a membrane electrode assembly including the polymer electrolyte membrane.
- the present disclosure provides a fuel cell including the membrane electrode assembly.
- the fuel cell of the present specification includes a fuel cell generally known in the art.
- a stack including a separator interposed between the membrane electrode assembly and the membrane electrode assembly; A fuel supply unit supplying fuel to the stack; And it provides a fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
- the fuel cell includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80.
- the stack 60 includes one or more membrane electrode assemblies, and when two or more membrane electrode assemblies are included, the stack 60 includes a separator interposed therebetween.
- the separator prevents the membrane electrode assemblies from being electrically connected to each other and transfers fuel and an oxidant supplied from the outside to the membrane electrode assembly.
- the oxidant supply unit 70 serves to supply the oxidant to the stack 60.
- Oxygen is typically used as the oxidizing agent, and may be used by injecting oxygen or air into the pump 70.
- the fuel supply unit 80 supplies fuel to the stack 60, and a fuel tank 81 storing fuel and a pump 82 supplying fuel stored in the fuel tank 81 to the stack 60. It can be configured as.
- the fuel may be gas or liquid hydrogen or hydrocarbon fuel, and examples of the hydrocarbon fuel include methanol, ethanol, propanol, butanol or natural gas.
- sulfonated polyether-etherketone-based ion conductive polymer was dissolved in DMSO (Dimethyl Sulfoxide) at a concentration of 7 wt% to form an impregnation solution, and a porosity of about 70% fixed to a frame of 10 cm ⁇ 10 cm, A polypropylene-based support having a thickness of about 15 ⁇ m was impregnated into the impregnation solution. After drying for 24 hours at 80 °C oven to prepare a polymer electrolyte membrane. The prepared polymer electrolyte membrane was acid-treated in 10% sulfuric acid at 80 ° C. for 24 hours, washed four times or more with distilled water, and dried.
- DMSO Dimethyl Sulfoxide
- the final thickness of the polymer electrolyte membrane prepared according to Example 1 was 9.7 ⁇ m to 12.2 ⁇ m, the thickness of the mixed layer was 7 ⁇ m to 8 ⁇ m, the thickness of the pure layer provided on the mixed layer is 0.7 ⁇ m to 1.2 ⁇ m, the mixed layer The thickness of the pure layer provided at the bottom was 2 ⁇ m to 3 ⁇ m.
- Example 2 Using only the impregnation solution used in Example 1, cast on a glass plate with a thickness of 400 ⁇ m, then dried in an oven at 80 °C for 24 hours to prepare a polymer electrolyte membrane.
- the prepared polymer electrolyte membrane was used in the same manner as in Example 1. Specifically, the polymer electrolyte membrane prepared according to Comparative Example 1 consists of only a pure layer, the thickness was 20 ⁇ m.
- PTFE polytetrafluoroethylene
- a fluorine-based support having a porosity of about 90% and a thickness of about 7 ⁇ m fixed to a frame of 10 cm ⁇ 10 cm. Further, the fluorine-based support was impregnated into the impregnation solution used in Example 1. Since the manufacturing process was the same as in Example 1.
- the final thickness of the polymer electrolyte membrane prepared according to Comparative Example 2 was 23 ⁇ m to 31 ⁇ m, the thickness of the mixed layer was 5 ⁇ m to 10 ⁇ m, the thickness of the pure layer provided on top of the mixed layer is 16 ⁇ m to 18 ⁇ m, The thickness of the pure layer provided below the mixed layer was 2 ⁇ m to 3 ⁇ m.
- the polymer electrolyte membranes prepared according to Example 1, Comparative Example 1 and Comparative Example 2 were measured for durability through an RH cycle, which is illustrated in FIG. 6.
- the x-axis refers to the number of cycles of the RH
- the y-axis refers to the crossover value of hydrogen to know the degree of damage to the polymer electrolyte membrane during the RH cycle.
- the polymer electrolyte membranes according to Comparative Examples 1 and 2 may not function properly due to damage of the electrolyte membrane from the beginning of the RH cycle.
- the polymer electrolyte membrane according to Example 1 does not cause damage to the electrolyte membrane even if the RH cycle exceeds 50,000 times.
- Example 1 Tensile strength of the polymer electrolyte membrane prepared according to Example 1 and Comparative Examples 1 and 2 was measured. Specifically, the prepared polymer electrolyte membrane was cut out three in the machine direction and the vertical direction in the machine direction in the form of an ASTM D-412A dog bone, and tensile strength tests were performed using a Shimadzu AGS-X 100N device. . The experiment was conducted at a temperature of 20 ° C. and a humidity of 22% at a distance of 100 mm and a tensile speed of 10 mm / min. The results according to Experimental Example 1 are shown in Table 1 below.
- the polymer electrolyte membrane prepared in Example 1 in the fuel cell was cut into a rectangle of 8 cm ⁇ 8 cm, and Pt 0.4 mg / cm 2 was applied to the upper and lower surfaces of the polymer electrolyte membrane.
- the carbon supported platinum catalyst was transferred to a size of 5 cm ⁇ 5 cm to prepare a membrane-electrode assembly.
- Performance evaluation was carried out at 70 °C, relative humidity (RH) 50%, H 2 / Air, atmospheric pressure conditions.
- Figure 7 shows the voltage according to the current density of the membrane electrode assembly prepared according to Experimental Example 2.
Abstract
Description
기계방향 | 기계방향의 수직방향 | |||
최대 응력(kgf/㎠) | 최대 신율(%) | 최대 응력(kgf/㎠) | 최대 신율(%) | |
실시예 1 | 919.3 | 72.7 | 832.7 | 49.4 |
1046.5 | 71.8 | 771.8 | 35.7 | |
986.1 | 69 | 905.6 | 55 | |
비교예 1 | 672 | 12.9 | 702.8 | 12.5 |
673.8 | 12.3 | 685.7 | 6.7 | |
733.1 | 38.5 | 692 | 11.5 | |
비교예 2 | 249.0 | 2.8 | 469.6 | 10.3 |
308.0 | 8.6 | 482.1 | 8.8 | |
432.4 | 4.9 | 373.7 | 4.1 |
Claims (26)
- 이온 이동 영역 및 3차원 망상 구조의 지지체를 포함하는 혼합층을 포함하고,상기 이온 이동 영역은 탄화수소계 이온 전도성 물질을 포함하는 2 이상의 셀이 3차원적으로 접하는 구조를 가지며,RH 사이클의 한계치가 적어도 20,000 회인 고분자 전해질막.
- 이온 이동 영역 및 3차원 망상 구조의 지지체를 포함하는 혼합층을 포함하고,상기 이온 이동 영역은 탄화수소계 이온 전도성 물질을 포함하는 2 이상의 셀이 3차원적으로 접하는 구조를 가지는 고분자 전해질막으로서,상기 고분자 전해질막의 기계방향(MD: Machine Direction)에서의 최대 응력은 200 kgf/㎠ 이상인 것인 고분자 전해질막.
- 이온 이동 영역 및 3차원 망상 구조의 지지체를 포함하는 혼합층을 포함하고,상기 이온 이동 영역은 탄화수소계 이온 전도성 물질을 포함하는 2 이상의 셀이 3차원적으로 접하는 구조를 가지는 고분자 전해질막으로서,상기 고분자 전해질막의 기계방향(MD: Machine Direction)의 수직방향에서의 최대 응력은 200 kgf/㎠ 이상인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 고분자 전해질막의 기계방향(MD: Machine Direction)에서의 최대 신율은 20 % 이상인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 고분자 전해질막의 기계방향(MD: Machine Direction)의 수직방향에서의 최대 신율은 10 % 이상인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 탄화수소계 물질은 측쇄에 1 이상의 양이온 교환기를 갖는 고분자이고,상기 고분자에 포함된 탄소 원자수와 불소 원자수의 비는 1:0 이상 1:1 미만이며,상기 양이온 교환기는 설폰산기, 카르복실산기, 인산기, 포스포닌산기 및 이들의 유도체로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 이온 전도성 물질은 술폰화 벤즈이미다졸계 고분자, 술폰화 폴리이미드계 고분자, 술폰화 폴리에테르이미드계 고분자, 술폰화 폴리페닐렌설파이드계 고분자, 술폰화 폴리술폰계 고분자, 술폰화 폴리에테르술폰계 고분자, 술폰화 폴리에테르케톤계 고분자, 술폰화 폴리에테르-에테르케톤계 고분자, 술폰화 폴리페닐퀴녹살린계 고분자, 및 술폰화 부분불소계가 도입된 고분자로 이루어진 군에서 선택되는 1종 또는 2종 이상을 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 지지체는 탄화수소계 물질을 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 지지체는 반 결정질 폴리머를 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 지지체는 폴리올레핀, 폴리아미드, 폴리에스터, 폴리아세탈(또는 폴리옥시메틸렌), 폴리설파이드, 폴리비닐 알코올, 이들의 코폴리머 및 이들의 조합을 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 혼합층의 전체 부피에 대하여 상기 이온 이동 영역은 40 부피% 이상 85 부피% 이하인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 이온 이동 영역은 상기 이온 전도성 물질을 60 부피% 이상 100 부피% 이하로 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 혼합층의 두께는 1 ㎛ 이상 30 ㎛ 이하인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 셀의 최대 직경의 평균은 0.25 ㎛ 이상 0.4 ㎛ 이하이고, 상기 셀의 최대 직경의 표준편차는 0.05 ㎛ 이상 0.2 ㎛ 이하인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 고분자 전해질막의 상면과 수평한 임의의 면에서, 상기 셀은 어느 한 방향(x축 방향) 및 이에 수직인 방향(y축 방향)과 고분자 전해질막의 두께 방향(z축 방향)으로 2층 이상 적층된 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 지지체는 2 이상의 상기 셀이 분포하는 스펀지 구조인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 고분자 전해질막의 수직 단면 및 수평 단면 모두에 2 이상의 상기 셀의 단면을 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 지지체는 2 이상의 노드(node)로 이루어지며, 각각의 노드는 3 이상의 분지를 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 혼합층은 임의의 1 ㎛3 영역에 10 이상 400 이하의 셀을 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 고분자 전해질막은 상기 혼합층만으로 이루어진 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 고분자 전해질막은 혼합층 상면, 또는 하면, 또는 상면 및 하면에 구비된 상기 이온 전도성 물질만을 포함하는 순수층을 더 포함하는 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 혼합층의 어느 일 면에 구비된 상기 순수층의 두께는 각각 독립적으로 0 ㎛ 초과 6 ㎛ 이하인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 고분자 전해질막의 전체 두께는 3 ㎛ 이상 36 ㎛ 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항에 있어서,상기 고분자 전해질막의 공기 투과도는 1hour/100㎖ 이상인 것인 고분자 전해질막.
- 청구항 1 내지 3 중 어느 한 항의 고분자 전해질막을 포함하는 막전극 접합체.
- 청구항 25의 막전극 접합체를 포함하는 연료전지.
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JP2016506263A JP2016519398A (ja) | 2013-04-29 | 2014-04-29 | 高分子電解質膜、高分子電解質膜を含む膜電極接合体および膜電極接合体を含む燃料電池 |
CN201480023430.3A CN105144454B (zh) | 2013-04-29 | 2014-04-29 | 聚合物电解质膜,包括该聚合物电解质膜的膜电极组件和包括该膜电极组件的燃料电池 |
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PCT/KR2014/003805 WO2014178621A1 (ko) | 2013-04-29 | 2014-04-29 | 고분자 전해질막, 고분자 전해질막을 포함하는 막전극 접합체 및 막 전극 접합체를 포함하는 연료전지 |
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KR102140121B1 (ko) | 2016-07-01 | 2020-07-31 | 주식회사 엘지화학 | 다공성 기재를 포함하는 강화-복합 전해질막 및 이의 제조방법 |
JP6839418B2 (ja) * | 2017-06-02 | 2021-03-10 | 株式会社デンソー | 燃料電池用電解質の製造方法 |
JP6771071B2 (ja) * | 2018-06-15 | 2020-10-21 | 日本碍子株式会社 | 電気化学セル用電解質及び電気化学セル |
JP6721762B2 (ja) * | 2018-06-15 | 2020-07-15 | 日本碍子株式会社 | 電気化学セル |
CN114730901A (zh) * | 2019-12-26 | 2022-07-08 | 可隆工业株式会社 | 聚合物电解质膜、包括其的膜-电极组件和测量其耐久性的方法 |
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EP2960976B1 (en) | 2018-04-25 |
CN105144454B (zh) | 2017-08-11 |
EP2960974A4 (en) | 2016-11-02 |
JP2016519397A (ja) | 2016-06-30 |
KR20140128894A (ko) | 2014-11-06 |
KR101579001B1 (ko) | 2015-12-18 |
US20160064764A1 (en) | 2016-03-03 |
JP6395272B2 (ja) | 2018-09-26 |
CN105144454A (zh) | 2015-12-09 |
KR20140128895A (ko) | 2014-11-06 |
EP2960976A1 (en) | 2015-12-30 |
EP2960975A1 (en) | 2015-12-30 |
CN105283993A (zh) | 2016-01-27 |
CN105283993B (zh) | 2018-06-15 |
EP2960974B1 (en) | 2018-02-21 |
EP2960975B1 (en) | 2018-05-30 |
KR20140128893A (ko) | 2014-11-06 |
US20160056488A1 (en) | 2016-02-25 |
US20160072144A1 (en) | 2016-03-10 |
US9991539B2 (en) | 2018-06-05 |
KR20160150081A (ko) | 2016-12-28 |
EP2960976A4 (en) | 2016-08-24 |
JP2016519398A (ja) | 2016-06-30 |
WO2014178621A1 (ko) | 2014-11-06 |
JP2016518005A (ja) | 2016-06-20 |
WO2014178619A1 (ko) | 2014-11-06 |
EP2960975A4 (en) | 2016-08-17 |
EP2960974A1 (en) | 2015-12-30 |
CN105164842A (zh) | 2015-12-16 |
US10050294B2 (en) | 2018-08-14 |
CN105164842B (zh) | 2019-04-19 |
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