WO2015080475A1 - 고분자 전해질막, 고분자 전해질막을 포함하는 막 전극 접합체 및 막 전극 접합체를 포함하는 연료전지 - Google Patents
고분자 전해질막, 고분자 전해질막을 포함하는 막 전극 접합체 및 막 전극 접합체를 포함하는 연료전지 Download PDFInfo
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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
- H01M8/1041—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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- 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
- H01M8/1025—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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- 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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- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- 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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- H01M8/1065—Polymeric electrolyte materials characterised by the form, e.g. perforated or wave-shaped
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- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
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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
- H01M8/103—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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- H01M8/102—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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- 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 uses less fuel, and has a merit 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 application fields ranging from mobile power sources for portable devices, transportation power sources for automobiles, and the like to distributed power generation 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 perfluorinated polymer electrolyte membrane, Asahi Chemicals' Aciplex-S membrane, Dow Chemical's Dow membrane and 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.
- the present specification includes a mixed layer including an ion transport region and a support of a three-dimensional network structure, wherein the ion transport region is a structure in which two or more cells including a first ion conductive polymer are three-dimensionally contacted, and the first ion IEC (ion exchange capacity) of the conductive polymer provides a polymer electrolyte membrane, characterized in that 1.7 meq / g or more and 2.5 meq / g or less.
- the present disclosure provides a membrane electrode assembly including the polymer electrolyte membrane.
- the present disclosure provides a fuel cell including the membrane electrode assembly.
- the polymer electrolyte membrane according to the present specification has an advantage of excellent durability. Specifically, when used in a fuel cell using a membrane electrode assembly comprising a polymer electrolyte membrane according to the present disclosure, it can contribute to the performance improvement of the fuel cell. That is, the high temperature humidification and drying is repeated to minimize the deterioration of the performance of the fuel electronics in the operating environment of the fuel cell in which the shrinkage and expansion of the polymer electrolyte membrane is repeated, thereby maintaining a constant performance.
- the polymer electrolyte membrane according to the present specification has excellent durability and high ionic conductivity. That is, the polymer electrolyte membrane according to the present disclosure minimizes the decrease in the ionic conductivity by including the support, and has the same level of ionic conductivity as in the absence of the support.
- 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 one embodiment of the present specification.
- Figure 5 shows the voltage according to the current density in the fuel cell of the polymer electrolyte membrane according to the embodiment and the comparative example at 100% relative humidity (RH) conditions.
- Figure 6 shows the voltage according to the current density in the fuel cell of the polymer electrolyte membrane according to the embodiment and the comparative example at 50% relative humidity (RH).
- the present specification includes a mixed layer including an ion transport region and a support of a three-dimensional network structure, wherein the ion transport region is a structure in which two or more cells including a first ion conductive polymer are three-dimensionally contacted, and the first ion IEC (ion exchange capacity) of the conductive polymer provides a polymer electrolyte membrane, characterized in that 1.7 meq / g or more and 2.5 meq / g or less.
- the first ion-conducting polymer may be included in the ion migration region to increase ion performance in the mixed layer due to high ion conductivity, thereby improving performance of the polymer electrolyte membrane.
- the mixed layer may be formed by impregnating the support with the first ion conductive polymer.
- a polymer electrolyte membrane without an additional pure layer may be formed.
- a polymer electrolyte membrane having an additional pure layer is provided on the upper and / or lower surface of the mixed layer. can do.
- the polymer electrolyte membrane includes a pure layer including a top surface, a bottom surface, or a second ion conductive polymer provided on the top and bottom surfaces of the mixed layer,
- the ion exchange capacity (IEC) may be lower than the ion exchange capacity (IEC) of the first conductive polymer.
- the pure layer may be provided on the upper and / or lower surface of the mixed layer, or may be provided on the additional pure layer.
- the ion exchange capacity (IEC) of the second ion conductive polymer may be 0.2 meq / g or more lower than the ion exchange capacity (IEC) of the first ion conductive polymer.
- the second ion conductive polymer may be provided on at least one surface of the mixed layer to prevent dissolution of the first ion conductive polymer contained in the mixed layer.
- the first ion conductive polymer may be eluted by moisture, and the second ion conductive polymer is eluted by water of the first ion conductive polymer. It can play a role to prevent this.
- the ion exchange capacity (IEC) of the second ion conductive polymer may be 0.9 meq / g or more and 1.8 meq / g or less.
- the pure layer may further include an additional pure layer including the first ion conductive polymer provided in contact with the mixed layer.
- the additional pure layer may be one in which the same polymer as the first ion conductive polymer included in the ion migration region is provided in contact with an upper portion, a lower portion, or an upper portion and a lower portion of the mixed layer.
- the support may be impregnated in the first ion conductive polymer, and the first ion conductive polymer may remain on the upper and / or lower surfaces of the mixed layer to form an additional pure layer.
- the polymer electrolyte membrane according to the present specification has excellent durability and high ionic conductivity. Specifically, the polymer electrolyte membrane according to the present disclosure minimizes the decrease in ionic conductivity according to the inclusion of the support, and has the same level of ionic conductivity as in the absence of the support. Therefore, the fuel cell including the polymer electrolyte membrane according to the present disclosure can minimize the damage of the electrolyte membrane due to long time driving, and further, can exhibit high performance.
- the thickness of the mixed layer may be 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 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 formed of only the mixed layer.
- the thicknesses of the pure layers provided on one surface of the mixed layer may be each independently greater than 0 ⁇ m and less than or equal to 6 ⁇ m.
- the thickness of the additional pure layer may be greater than 0 ⁇ m and 5 ⁇ m or less.
- the thickness of the pure layer may be to include the thickness of the additional pure layer.
- 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 the exemplary embodiment of the present specification, when the thickness difference between the pure layers is 0%, 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 of repeated humidification and drying.
- the total thickness of the polymer electrolyte membrane may be 3 ⁇ m or more and 36 ⁇ m or less.
- the ion migration region may be 40 vol% or more and 85 vol% or less with respect to the total volume of the mixed layer.
- the ion migration region may be 40 vol% or more and 80 vol% or less with respect to the total volume of the ion migration region and the support.
- the ion migration region may be 40 vol% or more and 70 vol% 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 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 specification may be spherical or spherical in shape, 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 intersect.
- 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 polymer surrounded by fibrous branches of a support, and the horizontal and vertical cross-sections of the virtual three-dimensional closed space in the case of being enclosed by the fibers of the support are 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 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-axis direction) may be stacked two or more layers.
- the support may be a sponge structure in which two or more of the cells are distributed.
- the support may have a structure in which the cells are regularly distributed. Specifically, according to one embodiment of the present specification, the support may have a variation in porosity of any unit volume within 10%.
- two or more cross sections of the cell may be included in both the vertical cross section and the horizontal cross section of the polymer electrolyte membrane.
- 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 500 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 500 nm or less.
- the ratio of the number of cells per 100 ⁇ mm 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 in the vertical section and the horizontal section per 100 ⁇ mm 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 greater than or equal to 40 nm and less than or equal to 500 nm.
- the standard deviation of the diameter of the cross section of the cell may be 50 nm to 200 nm.
- the cell may have a diameter of 40 nm or more and 1000 nm or less.
- the cross section of the cell may occupy 50% to 90% of the total cross-sectional area.
- the support consists of two or more nodes, and each node may include three or more branches.
- the distance between 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 250 nm.
- the ion migration region may include three or more inflection points per ⁇ m when the ions move.
- the inflection point may be tortuosity factors and may be expressed as three or more flexure factors per ⁇ m.
- the support may include a hydrocarbon-based or fluorine-based material.
- the support may include a semi-crystalline polymer.
- the semi-crystalline polymer of the present specification may have a range of 20 to 80% of the crystallinity.
- the semi-crystalline polymer is polyolefin, fluorocarbon, polyamide, polyester, polyacetal (or polyoxymethylene), polysulfide, polyvinyl alcohol, copolymers thereof and combinations thereof It may include, but 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 fluorocarbons are polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), florinated ethylene propylene (FEP), ethylene chlorotrifluoroethylene (ECTFE), ethylene tetrafluoroethylene (ETFE) ), Polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), prefluoroalkoxy (PFZ) resin, copolymers and blends thereof, but are not limited thereto.
- PTFE polytetrafluoroethylene
- PCTFE polychlorotrifluoroethylene
- FEP florinated ethylene propylene
- ECTFE ethylene chlorotrifluoroethylene
- ETFE ethylene tetrafluoroethylene
- PVDF Polyvinylidene fluoride
- PVF polyvinyl fluoride
- PFZ prefluoroalkoxy
- 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 crystalline polymer (LCP) ), but is not limited thereto.
- PET polyester terephthalate
- PBT polybutylene terephthalate
- PCT poly-1-4-cyclohexylenedimethylene terephthalate
- PEN polyethylene naphthalate
- LCP liquid crystalline polymer
- Such polysulfides include, but are not limited to, polyphenylsulfides, polyethylene sulfides, copolymers thereof and blends thereof.
- the polyvinyl alcohol includes, but is not limited to, ethylene-vinyl alcohol, copolymers thereof and blends thereof.
- the ion conductive polymer may include a cationic conductive polymer and / or an anionic conductive polymer.
- the ion conductive polymer may include a proton conductive material.
- the first ion conductive polymer and the second ion conductive polymer are sulfonated benzimidazole polymers, sulfonated polyimide polymers, sulfonated polyetherimide polymers, and sulfonated polyethers, respectively.
- Phenylene sulfide polymer sulfonated polysulfone polymer, sulfonated polyether sulfone polymer, sulfonated polyether ketone polymer, sulfonated polyether-ether ketone polymer, sulfonated polyphenylquinoxaline polymer, sulfonated It may include one or two or more selected from the group consisting of a partially fluorine-based polymer and a sulfonated fluorine-based polymer.
- the ion conductive polymer may have an ion conductivity of 1 mS / cm or more at 60 ° C. or more.
- the air permeability of the polymer electrolyte membrane may be 6 sec / 100 ml or more.
- the ion migration region may include 70% by volume or more and 100% by volume or less of the first ion conductive polymer.
- the polymer electrolyte membrane of the present specification has an advantage of excellent tensile strength and elongation.
- the tensile strength and elongation of the present specification means that the polymer electrolyte membrane of the dogbone form cut according to the American Society for Testing and Materials (ASTM) standard is measured at a speed of 10 mm / min with a united test machine (UTM).
- ASTM American Society for Testing and Materials
- the UTM is a device for simultaneously measuring tensile strength and elongation, and is generally used in the art.
- the tensile strength of the polymer electrolyte membrane may be 200 kgf / cm 2 or more and 2000 kgf / cm 2 or less, or 500 kgf / cm 2 or more and 1500 kgf / cm 2 or less.
- the elongation of the polymer electrolyte membrane may be 50% or more and 300% or less.
- the elongation of the polymer electrolyte membrane may be 100% or more and 300% or less.
- the polymer electrolyte membrane of the present specification has an advantage of excellent durability. Specifically, the polymer electrolyte membrane can be confirmed excellent durability through the RH cycle.
- the RH cycle of the present specification means that the electrolyte membrane is made of MEA (membrane electrode assembly) and the durability of the fuel cell is measured. Specifically, in the RH cycle of the present specification, 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, humidification of RH 150%, and RH 0% of non-humidity is converted every two minutes, which means measuring durability.
- MEA membrane electrode assembly
- the higher the RH cycle of the present specification the higher the durability of the electrolyte membrane.
- the RH cycle means the number of cycles until the damage occurred such that the electrolyte membrane cannot be used as the MEA.
- 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, it is considered that there is a damage to the electrolyte membrane, and the degree of damage to the electrolyte membrane can be determined according to the degree of increase of the crossover value of hydrogen.
- the polymer electrolyte membrane of the present specification can maintain a constant performance with almost no performance degradation even when the RH cycle is 20,000 or more.
- the RH cycle of the polymer electrolyte membrane may be 20,000 or more times. Furthermore, the RH cycle of the polymer electrolyte membrane of the present specification may be 40,000 or more, or 50,000 or more. In addition, the RH cycle of the polymer electrolyte membrane of the present specification may be 75,000 or more, or 80,000 or more. The polymer electrolyte membrane does not deteriorate even in the number of RH cycles in the above range.
- the RH cycle of the polymer electrolyte membrane may be 200,000 times or less.
- the RH cycle of the polymer electrolyte membrane may be 150,000 or less, or 100,000 or less.
- the RH cycle of the polymer electrolyte membrane may be one or more times and 150,000 or less times.
- the RH cycle of the polymer electrolyte membrane may be 20,000 or more and 150,000 or less.
- the RH cycle of the polymer electrolyte membrane may be 40,000 or more and 150,000 or less.
- the RH cycle of the polymer electrolyte membrane may be 50,000 or more and 150,000 or less.
- the RH cycle of the polymer electrolyte membrane may be 70,000 or more and 150,000 or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 30 ⁇ m or less, and the RH cycle may be 20,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 30 ⁇ m or less, and the RH cycle may be 40,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 30 ⁇ m or less, and the RH cycle may be 50,000 or more and 150,000 or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 30 ⁇ m or less, and the RH cycle may be 70,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 15 ⁇ m or less, and the RH cycle may be 20,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 15 ⁇ m or less, and the RH cycle may be 40,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 15 ⁇ m or less, and the RH cycle may be 50,000 or more and 150,000 or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 15 ⁇ m or less, and the RH cycle may be 70,000 or more and 150,000 times or less.
- the thickness of the entire pure layer of the polymer electrolyte membrane may be 0 ⁇ m or more and 10 ⁇ m or less, and the RH cycle may be 20,000 or more and 150,000 times or less.
- the thickness of the entire pure layer of the polymer electrolyte membrane may be 0 ⁇ m or more and 10 ⁇ m or less, and the RH cycle may be 40,000 or more and 150,000 times or less.
- the thickness of the entire pure layer of the polymer electrolyte membrane may be 0 ⁇ m or more and 10 ⁇ m or less, and the RH cycle may be 50,000 or more and 150,000 or less.
- the thickness of the entire pure layer of the polymer electrolyte membrane may be 0 ⁇ m or more and 10 ⁇ m or less, and the RH cycle may be 70,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane is 1 ⁇ m or more and 30 ⁇ m or less
- the thickness of the entire pure layer is 0 ⁇ m or more and 10 ⁇ m or less
- the RH cycle may be 20,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane is 1 ⁇ m or more and 30 ⁇ m or less
- the thickness of the entire pure layer is 0 ⁇ m or more and 10 ⁇ m or less
- the RH cycle may be 40,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane may be 1 ⁇ m or more and 30 ⁇ m or less, the thickness of the entire pure layer may be 0 ⁇ m or more and 10 ⁇ m or less, and the RH cycle may be 50,000 or more and 150,000 or less. have.
- the thickness of the mixed layer of the polymer electrolyte membrane is 1 ⁇ m or more and 30 ⁇ m or less
- the thickness of the entire pure layer is 0 ⁇ m or more and 10 ⁇ m or less
- the RH cycle may be 70,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane is 1 ⁇ m or more and 15 ⁇ m or less
- the thickness of the entire pure layer is 0 ⁇ m or more and 10 ⁇ m or less
- the RH cycle may be 20,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane is 1 ⁇ m or more and 15 ⁇ m or less
- the thickness of the entire pure layer is 0 ⁇ m or more and 10 ⁇ m or less
- the RH cycle may be 40,000 or more and 150,000 times or less.
- the thickness of the mixed layer of the polymer electrolyte membrane is 1 ⁇ m or more and 15 ⁇ m or less
- the thickness of the entire pure layer is 0 ⁇ m or more and 10 ⁇ m or less
- the RH cycle may be 50,000 or more and 150,000 or less.
- the thickness of the mixed layer of the polymer electrolyte membrane is 1 ⁇ m or more and 15 ⁇ m or less
- the thickness of the entire pure layer is 0 ⁇ m or more and 10 ⁇ m or less
- the RH cycle may be 70,000 or more and 150,000 times or less.
- 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 serves to prevent the membrane electrode assemblies from being electrically connected and to transfer fuel and 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.
- An impregnation solution was prepared by dissolving a hydrocarbon-based polymer having an IEC (ion exchange capacity) of 2.16 meq / g at 7 wt% in dimethyl sulfoxide (DMSO).
- the impregnation solution was impregnated with a support having a three-dimensional network structure in which two or more cells having a thickness of about 5 ⁇ m and a porosity of about 80% are regularly distributed. Thereafter, the mixture was dried in an oven at 80 ° C. for 24 hours to prepare a mixed layer.
- a solution prepared by dissolving a hydrocarbon-based polymer having an IEC (ion exchange capacity) of 1.81 meq / g at 7 wt% in DMSO (dimethyl sulfoxide) was prepared and applied to the upper and lower surfaces of the mixed layer, followed by 24 hours in an oven at 80 ° C. It dried and formed the pure layer.
- the prepared polymer electrolyte membrane was acid-treated with 10% sulfuric acid at 80 ° C. for 24 hours, then rinsed four times with distilled water, and dried at 80 ° C. to prepare a polymer electrolyte membrane.
- the IEC (ion exchange capacity) of the hydrocarbon-based polymer included in the impregnation solution was 1.81 meq / g, and a polymer electrolyte membrane was prepared in the same manner as in Example 1 without further forming a pure layer.
- the IEC (ion exchange capacity) of the hydrocarbon-based polymer contained in the impregnation solution is 1.68 meq / g, and the support has an ePTFE structure having an irregular distribution of pores of about 5 ⁇ m in thickness and a porosity of 85% or more and which cannot be defined as a cell.
- a polymer electrolyte membrane was prepared in the same manner as in Example 1 without further forming a pure layer.
- a membrane electrode assembly including the polymer electrolyte membrane was prepared. Specifically, the polymer electrolyte membrane is cut into a rectangle of 8 cm ⁇ 8 cm, and a Pt 0.4 mg / cm 2 carbon supported platinum catalyst is transferred to a size of 5 cm ⁇ 5 cm on the upper and lower surfaces of the polymer electrolyte membrane to form a membrane electrode assembly.
- a membrane electrode assembly including the polymer electrolyte membrane was prepared. Specifically, the polymer electrolyte membrane is cut into a rectangle of 8 cm ⁇ 8 cm, and a Pt 0.4 mg / cm 2 carbon supported platinum catalyst is transferred to a size of 5 cm ⁇ 5 cm on the upper and lower surfaces of the polymer electrolyte membrane to form a membrane electrode assembly.
- Performance evaluation of the prepared membrane electrode assembly was performed under conditions of 100% relative humidity (RH), 50% relative humidity (RH), and 32% relative humidity (RH) under H 2 / Air and atmospheric pressure.
- Figure 5 shows the voltage according to the current density in the fuel cell of the polymer electrolyte membrane according to the embodiment and the comparative example at 100% relative humidity (RH) conditions.
- Figure 6 shows the voltage according to the current density in the fuel cell of the polymer electrolyte membrane according to the embodiment and the comparative example at 50% relative humidity (RH).
- the polymer electrolyte membrane according to the embodiment shows higher performance than the polymer electrolyte according to the comparative example.
- the polymer electrolyte membrane according to the embodiment is stable performance compared to the polymer electrolyte membrane according to the comparative example.
- the polymer electrolyte membrane according to the embodiment can realize stable performance under high humidification conditions, and when the pure layer is provided as in the polymer electrolyte membrane according to Example 1 It is more stable under humid conditions and can maintain excellent performance.
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Abstract
Description
Claims (28)
- 이온 이동 영역 및 3차원 망상 구조의 지지체를 포함하는 혼합층을 포함하고,상기 이온 이동 영역은 제1 이온 전도성 고분자를 포함하는 2 이상의 셀이 3차원적으로 접하는 구조이며,상기 제1 이온 전도성 고분자의 IEC(ion exchange capacity)는 1.7 meq/g 이상 2.5 meq/g 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 혼합층의 상면, 또는 하면, 또는 상면 및 하면 상에 구비된 제2 이온 전도성 고분자를 포함하는 순수층을 포함하고,상기 제2 이온 전도성 고분자의 IEC(ion exchange capacity)는 상기 제1 전도성 고분자의 IEC(ion exchange capacity)보다 낮은 것을 특징으로 하는 고분자 전해질막.
- 청구항 2에 있어서,상기 제2 이온 전도성 고분자의 IEC(ion exchange capacity)는 상기 제1 이온 전도성 고분자의 IEC(ion exchange capacity)보다 0.2 meq/g 이상 낮은 것을 특징으로 하는 고분자 전해질막.
- 청구항 2에 있어서,상기 제2 이온 전도성 고분자의 IEC(ion exchange capacity)는 0.9 meq/g 이상 1.8 meq/g 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 2에 있어서,상기 순수층은 혼합층에 접하여 구비된 상기 제1 이온 전도성 고분자를 포함하는 추가의 순수층을 더 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 혼합층의 두께가 1 ㎛ 이상 30 ㎛ 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 2에 있어서,상기 순수층의 두께는 각각 독립적으로 0 ㎛ 초과 6 ㎛ 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 5에 있어서,상기 추가의 순수층의 두께는 0 ㎛ 초과 5㎛ 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 2에 있어서,상기 혼합층의 상면 및 하면에 각각 구비된 상기 순수층 간의 두께 차이는 상기 혼합층 두께의 50 % 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 2에 있어서,상기 혼합층과 상기 전체 순수층의 두께 비율은 1:0 내지 1:4 인 것을 특징으로 하는 고분자 전해질막.
- 청구항 2에 있어서,상기 고분자 전해질막의 전체 두께는 3 ㎛ 이상 36 ㎛ 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 혼합층의 전체 부피에 대하여 상기 이온 이동 영역은 40 부피% 이상 85 부피% 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,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 2층이상 적층된 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 지지체는 2이상의 상기 셀이 분포하는 스펀지 구조인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 고분자 전해질막의 수직 단면 및 수평 단면 모두에 2 이상의 상기 셀의 단면을 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 지지체는 2 이상의 노드(node)로 이루어지며, 각각의 노드는 3이상의 분지를 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 이온 이동 영역은 이온의 이동시 1 ㎛당 3 이상의 변곡 지점을 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 지지체는 탄화수소계 또는 불소계 물질을 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 18에 있어서,상기 지지체는 반 결정질 폴리머를 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 18에 있어서,상기 지지체는 폴리올레핀, 플루오로카본, 폴리아미드, 폴리에스터, 폴리아세탈(또는 폴리옥시메틸렌), 폴리설파이드, 폴리비닐 알코올, 이들의 코폴리머 및 이들의 조합을 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 제1 이온 전도성 고분자 및 상기 제2 이온 전도성 고분자는 각각 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, 술폰화 부분불소계가 도입된 고분자 및 술폰화 불소계 고분자로 이루어진 군에서 선택되는 1종 또는 2종 이상을 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 고분자 전해질막의 공기 투과도는 6 sec/100 ㎖ 이상인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 이온 이동 영역은 상기 제1 이온 전도성 고분자를 70 부피% 이상 100 부피% 이하로 포함하는 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 고분자 전해질막의 인장강도는 200 kgf/㎠ 이상 2000 kgf/㎠ 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 고분자 전해질막의 신율(elongation)은 50 % 이상 300 % 이하인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1에 있어서,상기 고분자 전해질막의 RH 사이클은 20,000회 이상인 것을 특징으로 하는 고분자 전해질막.
- 청구항 1 내지 26 중 어느 한 항의 고분자 전해질막을 포함하는 막 전극 접합체.
- 청구항 27의 막 전극 접합체를 포함하는 연료전지.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US15/038,951 US10297852B2 (en) | 2013-11-26 | 2014-11-26 | Polymer electrolyte membrane, membrane electrode assembly comprising polymer electrolyte membrane, and fuel cell comprising membrane electrode assembly |
EP14865322.3A EP3076466B1 (en) | 2013-11-26 | 2014-11-26 | Polymer electrolyte membrane, membrane electrode assembly comprising polymer electrolyte membrane, and fuel cell comprising membrane electrode assembly |
CN201480071336.5A CN105849959B (zh) | 2013-11-26 | 2014-11-26 | 聚合物电解质膜、包括聚合物电解质膜的膜电极组合件及包括膜电极组合件的燃料电池 |
JP2016534223A JP6316964B2 (ja) | 2013-11-26 | 2014-11-26 | 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 |
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KR10-2013-0144444 | 2013-11-26 | ||
KR20130144444 | 2013-11-26 |
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WO2015080475A1 true WO2015080475A1 (ko) | 2015-06-04 |
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CN111635531A (zh) * | 2020-05-28 | 2020-09-08 | 珠海冠宇电池股份有限公司 | 一种聚烯烃接枝苯并咪唑类聚合物质子交换膜及其制备方法与应用 |
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KR20140128895A (ko) * | 2013-04-29 | 2014-11-06 | 주식회사 엘지화학 | 고분자 전해질막, 고분자 전해질막을 포함하는 막전극 접합체 및 막 전극 접합체를 포함하는 연료전지 |
KR102130873B1 (ko) | 2016-06-01 | 2020-07-06 | 주식회사 엘지화학 | 강화막, 이를 포함하는 막 전극 접합체 및 연료 전지, 및 이의 제조방법 |
CN108461792B (zh) * | 2016-12-13 | 2021-11-30 | 中国科学院大连化学物理研究所 | 一种复合型碱性聚合物电解质膜及其制备方法和应用 |
KR102293177B1 (ko) * | 2017-11-30 | 2021-08-26 | 코오롱인더스트리 주식회사 | 고분자 전해질 막, 이의 제조 방법 및 이를 포함하는 막 전극 어셈블리 |
KR102203974B1 (ko) | 2018-01-19 | 2021-01-15 | 주식회사 엘지화학 | 막 전극 접합체의 제조방법 및 적층체 |
KR102169843B1 (ko) | 2018-01-22 | 2020-10-26 | 주식회사 엘지화학 | 막 전극 접합체의 제조방법 및 적층체 |
KR102480909B1 (ko) | 2018-01-22 | 2022-12-22 | 주식회사 엘지화학 | 전극 제조장치 및 전극 제조방법 |
KR102586433B1 (ko) * | 2018-04-26 | 2023-10-06 | 현대자동차주식회사 | 연료전지용 전해질막의 제조방법 및 이로 제조된 전해질막 |
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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EP3076466A4 (en) | 2017-04-19 |
KR101727369B1 (ko) | 2017-04-14 |
EP3076466A1 (en) | 2016-10-05 |
CN105849959B (zh) | 2019-11-19 |
JP2016538698A (ja) | 2016-12-08 |
KR20150060599A (ko) | 2015-06-03 |
CN105849959A (zh) | 2016-08-10 |
US10297852B2 (en) | 2019-05-21 |
US20170005355A1 (en) | 2017-01-05 |
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