WO2011025259A2 - 연료전지용 고분자 전해질막 및 그 제조방법 - Google Patents
연료전지용 고분자 전해질막 및 그 제조방법 Download PDFInfo
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- WO2011025259A2 WO2011025259A2 PCT/KR2010/005699 KR2010005699W WO2011025259A2 WO 2011025259 A2 WO2011025259 A2 WO 2011025259A2 KR 2010005699 W KR2010005699 W KR 2010005699W WO 2011025259 A2 WO2011025259 A2 WO 2011025259A2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
- H01M8/0293—Matrices for immobilising electrolyte solutions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
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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
Definitions
- the present invention relates to an electrolyte membrane used for a fuel cell, and more particularly to a polymer electrolyte membrane.
- a fuel cell is a battery that converts chemical energy generated by oxidation of a fuel into electrical energy directly, and has been in the spotlight as a next-generation energy source due to its high energy efficiency and eco-friendly features with low emission of pollutants.
- a fuel cell generally has a structure in which an anode and a cathode are formed on both sides of an electrolyte membrane, and such a structure is called a membrane electrode assembly (MEA).
- MEA membrane electrode assembly
- Fuel cells can be classified into alkaline electrolyte fuel cells and polymer electrolyte fuel cells (PEMFC) according to the type of electrolyte membrane.
- PEMFC polymer electrolyte fuel cells
- polymer electrolyte fuel cells have a low operating temperature of less than 100 ° C. and fast start-up. Due to the advantages of over response characteristics and excellent durability, it has been spotlighted as a portable, vehicle, and home power supply.
- Such a polymer electrolyte fuel cell may include a hydrogen ion exchange membrane fuel cell (PEMFC) using hydrogen gas as a fuel.
- PEMFC hydrogen ion exchange membrane fuel cell
- the polymer electrolyte membrane is a passage through which hydrogen ions (H + ) generated from the anode are transferred to the cathode, the conductivity of the hydrogen ions (H + ) should be excellent.
- the polymer electrolyte membrane should have excellent separation ability to separate hydrogen gas supplied to the anode and oxygen supplied to the cathode, and also have excellent mechanical strength, dimensional stability, chemical resistance, and the like. Ohmic loss) should be small.
- the polymer electrolyte membrane currently used is a fluororesin, a perfluorosulfonic acid resin (hereinafter referred to as a fluorine-based ion conductor).
- fluorine-based ion conductors have a weak mechanical strength, so that when used for a long time, pinholes are generated, thereby lowering energy conversion efficiency.
- attempts have been made to increase the thickness of the fluorine-based ion conductor, but in this case, the resistance loss is increased, and the use of expensive materials is increased, thereby reducing the economic efficiency.
- Teflon resin porous polytetrafluoroethylene resin
- the hydrogen ion conductivity may be slightly lower than that of the polymer electrolyte membrane composed of the fluorine-based ion conductor alone, but the mechanical strength is relatively excellent, and thus the thickness of the electrolyte membrane can be reduced, thereby reducing the loss of resistance.
- Teflon resin has very low adhesiveness, the ion conductor selection is limited, and a product having a fluorine-based ion conductor has a disadvantage in that a fuel crossover phenomenon is larger than that of a hydrocarbon system.
- the price of not only the fluorine-based ion conductor but also the porous Teflon resin is expensive, it is required to develop a new material which is still inexpensive for mass production.
- the present invention has a high melting point, insoluble in organic solvents and excellent porosity of the nano-web filled with ion conductors under optimum conditions, the overall thickness can be reduced, the resistance loss
- the purpose of the present invention is to provide a polymer electrolyte membrane having the effect of reducing the material cost, reducing the heat resistance and lowering the thickness expansion rate, so that the ion conductivity does not decrease for a long time.
- a porous nano web having a melting point of 300 °C or more, insoluble in organic solvents of NMP, DMF, DMA, or DMSO at room temperature; And an ion conductor filled in the pores of the porous nanoweb and comprising a hydrocarbon-based material soluble in the organic solvent at room temperature.
- the polymer electrolyte membrane may have a thickness expansion ratio of 10% or less.
- the polymer electrolyte membrane may be characterized in that the thickness ratio of the nanoweb measured by the following formula is 20% or more.
- Thickness ratio of nano web [A / (B + C)] ⁇ 100
- A is the average thickness of the nanoweb
- B is the average thickness of the upper ion conductor
- C is the average thickness of the lower ion conductor.
- the nanoweb may comprise polyimide, polybenzoxazole, copolymers thereof or mixtures thereof.
- the nano web may be made of a nanofiber having an average diameter of 0.005 to 5 ⁇ m.
- the nanoweb is characterized in that it has an average thickness of 1 to 20 ⁇ m.
- the nanoweb may have a porosity of 50 to 98% and an average diameter of pores of 0.05 to 30 ⁇ m.
- the ion conductor is sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (S-PEEK), sulfonated polybenzimidazole (S-PBI), sulfonated polysulfone (sulfonated polysulfone) S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene or mixtures thereof.
- S-PI sulfonated polyimide
- S-PAES sulfonated polyarylethersulfone
- S-PEEK sulfonated polyetheretherketone
- S-PBI sulfonated polybenzimidazole
- S-PS sulfonated polysulfone
- S-PS sulfonated polystyrene
- the polymer electrolyte membrane may have a mechanical strength of 10 MPa or more.
- the present invention is a process for preparing a spinning solution by melting a precursor (precusor) in a spinning solvent; Electrospinning the spinning solution to prepare a porous nanoweb made of nanofibers having an average diameter of 0.005 to 5 ⁇ m; Post-processing the porous nanoweb such that the porous nanoweb is insoluble in an organic solvent of NMP, DMF, DMA, or DMSO; Preparing an ion conductor solution by dissolving an ion conductor including a hydrocarbon-based material soluble in the organic solvent in the organic solvent; And removing the organic solvent after filling the ion conductor solution in the pores of the post-processed porous nanoweb such that the thickness ratio of the nanoweb measured by the following equation is 20% or more.
- Thickness ratio of nano web [A / (B + C)] ⁇ 100
- A is the average thickness of the nanoweb
- B is the average thickness of the upper ion conductor
- C is the average thickness of the lower ion conductor.
- the precursor may comprise up to 0.5% by weight of moisture.
- the post-treatment process may include a heat treatment process or a chemical treatment process.
- the porous nanoweb may include polyimide or polybenzoxazole.
- the present invention has the following effects.
- the polymer electrolyte membrane according to the present invention is a structure in which the ion conductor is filled in the pores of the nanoweb which are excellent in heat resistance and insoluble in organic solvents under optimum conditions, the overall thickness of the electrolyte membrane can be reduced, thereby improving ion conductivity and resistance. The loss is reduced, and the thickness expansion ratio can be lowered, thereby maintaining the performance for a long time.
- the polymer electrolyte membrane according to the present invention is composed of both a hydrocarbon-based polymer material and the nanoweb and the ion conductor, there is an excellent effect of adhesion between both excellent durability.
- the polymer electrolyte membrane according to the present invention uses a relatively inexpensive hydrocarbon-based polymer material without using an expensive fluorine-based ion conductor or Teflon resin as in the prior art, it is excellent in economical efficiency in mass production.
- FIG. 1 is a cross-sectional view of a polymer electrolyte membrane according to an embodiment of the present invention.
- the polymer electrolyte membrane according to the present invention includes a porous nanoweb, and an ion conductor filled in pores of the porous nanoweb.
- the porous nanoweb serves to enhance the mechanical strength of the polymer electrolyte membrane and to promote morphological stability by inhibiting volume expansion by moisture.
- the porous nanoweb is made of a hydrocarbon-based polymer which is advantageous in terms of price.
- the porous nanoweb is insoluble in the organic solvent of NMP, DMF, DMA, or DMSO at room temperature, the process of filling the ion conductor in the nanoweb pores is easy. That is, in order to fill the ion conductor in the pores of the nanoweb, the ion conductor is dissolved in an organic solvent to prepare an ion conductor solution, and then the ion conductor solution is filled in the pores of the porous nanoweb, and the porous nanoweb is dissolved in the organic solvent. In this case, during the process of filling the ion conductor solution into the pores of the porous nanoweb, the nanoweb is dissolved to obtain a polymer electrolyte membrane having a desired structure.
- the porous nanoweb comprises a hydrocarbon-based material that is insoluble in organic solvents.
- the porous nanoweb includes a hydrocarbon-based material having a melting point of 300 ° C. or higher. As such, since the porous nanoweb has a high melting point, the porous nanoweb maintains a stable shape even in a high temperature environment and is not easily separated from the electrode.
- porous nanoweb examples include polyimide, polybenzoxazole, copolymers thereof, or mixtures thereof.
- the porous nanoweb consists of a three-dimensionally connected web consisting of a predetermined fiber, in this case the thickness of the fiber may be in the range of 0.005 to 5 ⁇ m. If the thickness of the fibers constituting the nano-web is less than 0.005 ⁇ m may decrease the mechanical strength of the porous nano-web, and if the thickness of the fiber exceeds 5 ⁇ m may not be easy to control the porosity of the porous nano-web.
- the porous nanoweb may be formed to a thickness of 5 to 20 ⁇ m.
- the thickness of the porous nanoweb is less than 5 ⁇ m, the mechanical strength and shape stability of the polymer electrolyte membrane may be reduced, and when the thickness of the porous nanoweb exceeds 20 ⁇ m, the resistance loss of the polymer electrolyte membrane may increase.
- the porous nanoweb may have a porosity of 70 to 98%.
- porosity of the porous nanoweb is less than 70%, the ionic conductivity of the polymer electrolyte membrane may drop, and when the porosity of the porous nanoweb exceeds 98%, the mechanical strength and shape stability of the polymer electrolyte membrane may decrease.
- the ion conductor performs an ion conducting function, which is a main function of the polymer electrolyte membrane, and can use a hydrocarbon-based polymer having such an ion conducting function and advantageous in terms of price, and as described above, the pores of the porous nanoweb.
- a hydrocarbon-based material soluble in an organic solvent is included.
- Hydrocarbon-based polymers that can satisfy all of these requirements can be used in ionic conductors such as sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (S-PEEK), and sulfonate polybenzimidazole (sulfonated polybenzimidazole: S-PBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene, or mixtures thereof.
- S-PI sulfonated polyimide
- S-PAES sulfonated polyarylethersulfone
- S-PEEK sulfonated polyetheretherketone
- polybenzimidazole sulfonated polybenzimidazole: S-PBI
- S-PSU sulfonated polysulfone
- the ion conductor is filled in the pores of the porous nanoweb, the adhesion between the ion conductor and the porous nanoweb may be degraded when the operating conditions such as temperature or humidity during fuel cell operation is changed, in the case of the present invention Since both the ion conductor and the porous nanoweb are composed of hydrocarbon-based polymers, the adhesion between the two is basically excellent.
- the hydrocarbon-based material included in the ion conductor and the hydrocarbon-based material included in the porous nanoweb may be composed of the same material system. Specifically, S-PI (sulfonated polyimide) is used as the ion conductor and as the porous nanoweb. If polyimide is used, the adhesion between the ion conductor and the porous nanoweb may be very excellent.
- the electrolyte membrane including these can inhibit expansion in three dimensions by moisture, so that the length and thickness expansion ratio are relatively low.
- the polymer electrolyte membrane including the porous nanoweb having excellent pore properties and the ion conductor sufficiently filled in the pores of the porous nanoweb has a thickness expansion ratio of 10% or less. That is, it may be preferable that the thickness expansion ratio of the degree of deformation in the thickness direction with respect to the moisture of the polymer electrolyte membrane is 10% or less.
- the polymer electrolyte membrane may be used in a fuel cell separator, and the separator repeats expansion and contraction as it is exposed to high humidity. If the thickness expansion ratio of the separator is too high, the separator may be separated from the electrode. If so, the performance of the fuel cell may be drastically degraded.
- the thickness expansion ratio of the polymer electrolyte membrane is measured from the following equation.
- Thickness Expansion Rate (%) [(T1-T0) / T0)] ⁇ 100
- T0 is the average thickness of the polymer electrolyte membrane before expansion in water
- T1 is the average thickness of the polymer electrolyte membrane after expansion in water.
- This thickness expansion ratio is most affected by the material of construction, but also greatly affected by the shape of the electrolyte membrane.
- the electrolyte membrane is a single membrane composed of only ion conductors, the membrane has a very high moisture content due to the ion conductor characteristics, and due to this characteristic, the single membrane is directly affected by moisture, and thus the thickness expansion ratio may be very large.
- the electrolyte membrane in which the ion conductor is filled in the web formed by entangled fibers in three dimensions can suppress expansion in three dimensions by moisture, so that the length and thickness expansion ratio are relatively low.
- the thickness expansion ratio of the electrolyte membrane is further lowered. Because the web serving as the support is usually hydrophobic, the expansion does not occur easily due to moisture, and the ion-conductor strongly attached to the web is affected by the water expansion characteristics of the web, thereby lowering the thickness expansion rate.
- the surface area, porosity, and orientation can have an optimal three-dimensional structure, and thus the electrolyte membrane prepared therefrom has a lower thickness expansion ratio.
- the polymer electrolyte membrane of the present invention uses a nanoweb having excellent surface area and porosity, which is prepared by laminating nanofibers under optimum conditions, and has a low thickness expansion rate of 10% or less because it consists of such nanoweb and strongly adhered ion conductors. Will have
- the polymer electrolyte membrane may have a thickness ratio of 20% or more as measured by the following formula.
- Thickness ratio of nano web [A / (B + C)] ⁇ 100
- A is the average thickness of the nanoweb
- B is the average thickness of the upper ion conductor
- C is the average thickness of the lower ion conductor.
- the thickness ratio of the nanoweb is less than 20%, as the support portion of the electrolyte membrane is too low, the mechanical properties may be drastically lowered, so durability may be greatly reduced, and battery performance decreases as the thickness expansion ratio is increased. Because it can be.
- the polymer electrolyte membrane according to the present invention has a structure in which the ion conductor is filled in the pores of the porous nanoweb, the mechanical strength is excellent to 10 MPa or more.
- the overall thickness of the polymer electrolyte membrane can be reduced to 80 ⁇ m or less, thereby increasing the ion conduction speed, reducing the resistance loss, and reducing the material cost.
- the porous nanoweb and the ion conductor constituting the polymer electrolyte membrane both use a hydrocarbon-based polymer material
- the present invention has excellent adhesive strength, and thus, durability is excellent, and in addition, the conventional fluorine-based ion conductor or Teflon resin, etc. Because of using a relatively inexpensive hydrocarbon-based polymer material without using a has a good economical advantage in mass production.
- a method of preparing a polymer electrolyte membrane includes a process of preparing a porous nanoweb containing a hydrocarbon-based material insoluble in an organic solvent, and an ion conductor solution by dissolving an ion conductor containing a hydrocarbon-based material insoluble in an organic solvent in an organic solvent. It includes the process of manufacturing.
- the porous nanoweb includes a hydrocarbon-based material that is insoluble in an organic solvent
- the porous nanoweb may be prepared through a predetermined reaction after forming the nanoweb using a precursor soluble in the organic solvent.
- a precursor is prepared by dissolving a precursor in a spinning solvent, followed by electrospinning the prepared spinning solution to prepare a porous nanoweb made of nanofibers having an average diameter of 0.005 to 5 ⁇ m.
- Porous nanowebs can be prepared by post-treatment of the nanowebs.
- the porous nanoweb is manufactured through an electrospinning process to obtain high porosity and fine pores and thin films.
- porous nano webs that are insoluble in organic solvents cannot be directly manufactured through an electrospinning process.
- the polyimide or polybenzoxazole forming the porous nanoweb is difficult to prepare a spinning solution because it is difficult to dissolve in a solvent of NMP, DMF, DMA, or DMSO.
- the precursor nanoweb is prepared by using a precursor that is well soluble in an organic solvent, and then the prepared precursor nanoweb is post-treated so that it is not dissolved in the organic solvent, thereby preparing a porous nanoweb which is insoluble in the organic solvent.
- the precursor has a moisture content of 0.5% or less. This is because, if the moisture content of the precursor exceeds 0.5%, the viscosity of the spinning solution may be lowered by the moisture, and the filament may be cut by the moisture after spinning, thereby decreasing processability and deteriorating physical properties by acting as a defect.
- the post-treatment method for preparing the precursor nanoweb into the insoluble porous nanoweb includes a heat treatment method or a chemical treatment method.
- the heat treatment method may be performed using a hot press set to a high temperature and a high pressure.
- the polyimide porous nanoweb may be prepared by electrospinning a polyamicacid precursor to form a nanoweb precursor and then imidizing the nanoweb precursor using a hot press.
- a precursor solution is prepared by dissolving polyamic acid in a tetrahydrofuran (THF) solvent, and the precursor solution is sprayed at a temperature of 20 to 100 ° C. and a high voltage of 1 to 1,000 kPa.
- the polyimide porous nanoweb may be completed by forming a polyamic acid nanoweb on a collector by discharging it and then heat treating the polyamic acid nanoweb in a hot press set at a temperature of 80 to 400 ° C.
- Polybenzoxazole porous nanoweb of another embodiment of the present invention by using a polyhydroxyamide (polyhydroxyamide) precursor can be prepared by an electrospinning and heat treatment in a similar manner as described above.
- the polyimide or polybenzoxazole porous nanoweb having a high melting point and insoluble in an organic solvent serves to improve heat resistance, chemical resistance, and mechanical properties of the electrolyte membrane.
- the ion conductor solution is filled in the pores of the porous nanoweb.
- the process of filling the ion conductor solution into the pores of the porous nanoweb may use a supporting process, but is not necessarily limited thereto, and various methods known in the art, such as a laminating process, a spray process, a screen printing process, a doctor blade process, and the like. Method can be used.
- the immersion process it is preferable to perform the immersion process 2 to 5 times for 5 to 30 minutes at room temperature.
- the organic solvent in the ion conductor solution is removed so that the ion conductor is filled in the pores of the porous nanoweb.
- the process of removing the organic solvent may be a process of drying for 2 to 5 hours in a 60 to 150 degree hot air oven.
- the polyamic acid / THF spinning solution having a concentration of 12% by weight was electrospun in a state where a voltage of 30 kV was applied, and then a polyamic acid nano web precursor was formed, followed by heat treatment in an oven at 350 ° C. for 15 hours Polyimide porous nanowebs with average thicknesses were prepared. At this time, the electrospinning was carried out in a state in which a voltage of 30 kW was applied in a spray jet nozzle at 25 °C.
- S-PEEK sulfonated polyetheretherketone
- NMP N-methyl-2-pyrrolidinone
- the porous nanoweb was immersed in the ion conductor solution. Specifically, the immersion process was performed three times at room temperature for 20 minutes. At this time, a reduced pressure atmosphere was applied for 1 hour to remove fine bubbles. Thereafter, the resultant was dried in a hot air oven maintained at 80 ° C. for 3 hours to remove NMP to prepare a polymer electrolyte membrane having an average thickness of 45 ⁇ m.
- Example 1 In Example 1 described above, except that the average thickness of the porous nanoweb is changed to 10 ⁇ m by adjusting the electrospinning conditions, and the average thickness of the electrolyte membrane is changed to 50 ⁇ m by adjusting the amount of ion conductor impregnation.
- a polymer electrolyte membrane was prepared in the same manner as in 1.
- S-PEEK sulfonated polyetheretherketone
- NMP N-methyl-2-pyrrolidinone
- a film was formed using a doctor blade on a glass plate and immersed in water at room temperature. This was again immersed in ultrapure water for one day to remove the residual solvent and dried for 24 hours in hot air maintained at 80 °C to prepare a porous polysulfone membrane of 30 ⁇ m thickness.
- the polysulfone porous membrane thus prepared was impregnated and dried in the same manner as in Example 1 to dry the Nafion solution in alcohol to prepare a polymer electrolyte membrane having an average thickness of 45 ⁇ m.
- Example 1 the electrospinning conditions were adjusted to change the average thickness of the porous nanoweb to 8 ⁇ m, and the average thickness of the polymer electrolyte membrane was changed to 50 ⁇ m by adjusting the amount of ion conductor impregnation.
- a polymer electrolyte membrane was prepared in the same manner as in Example 1.
- the thickness of the sample 10 points was measured using a micrometer to evaluate the thickness of the porous nanoweb and the polymer electrolyte membrane as an average value.
- the average thickness (A) of the nanoweb and the average thickness (B + C) of the ion conductor obtained through the cross-sectional photograph of the polymer electrolyte membrane obtained through the electron microscope, using the following equation, the thickness of the nanoweb The ratio was measured.
- Samples of 10 cm ⁇ 10 cm were prepared from the polymer electrolyte membranes obtained in Examples and Comparative Examples, and the thicknesses (T 0) were measured after vacuum drying each sample at 80 ° C. for 3 hours. Subsequently, each sample was immersed in water at room temperature for 3 hours, then taken out to remove the surface water, and then the thickness T1 was measured. Next, using the obtained sample thickness before and after swelling, the thickness expansion ratio (%) of the polymer electrolyte membrane was measured from the following equation.
- Thickness Expansion Rate (%) [(T1-T0) / T0)] ⁇ 100
- the electrolyte membrane of the present invention has excellent durability, ion conductivity, and low thickness expansion rate, the electrolyte membrane can be widely used in various fields such as a separator of a fuel cell.
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Abstract
Description
Claims (13)
- 300℃ 이상의 융점을 갖고, 상온에서 NMP, DMF, DMA, 또는 DMSO의 유기용매에 비용해성인 다공성 나노 웹; 및상기 다공성 나노 웹의 기공 내에 충진되고, 상온에서 상기 유기용매에 용해성인 탄화수소계 물질을 포함하는 이온전도체를 포함하는 고분자 전해질막.
- 제1항에 있어서,상기 고분자 전해질막은 10% 이하의 두께 팽창률을 갖는 것을 특징으로 하는 고분자 전해질막.
- 제1항에 있어서,상기 고분자 전해질막은 아래 식에 의해 측정된 상기 나노 웹의 두께 비율이 20% 이상인 것을 특징으로 하는 고분자 전해질막.나노 웹의 두께 비율 = [A/(B+C)]×100상기 A는 나노 웹의 평균 두께이고, 상기 B는 상부 이온전도체의 평균 두께이며, 상기 C는 하부 이온전도체의 평균 두께이다.
- 제1항에 있어서,상기 나노 웹은 폴리이미드(polyimide), 폴리벤즈옥사졸(polybenzoxazole), 그들의 공중합물 또는 그들의 혼합물을 포함하는 고분자 전해질막.
- 제1항에 있어서,상기 나노 웹은 0.005 내지 5 ㎛의 평균 직경을 갖는 나노 섬유로 이루어진 것을 특징으로 하는 고분자 전해질막.
- 제1항에 있어서,상기 나노 웹은 1 내지 20 ㎛의 평균 두께를 갖는 것을 특징으로 하는 고분자 전해질막.
- 제1항에 있어서,상기 나노 웹은 다공도가 50 내지 98 %이고 기공의 평균 직경이 0.05 내지 30 ㎛인 것을 특징으로 하는 고분자 전해질막.
- 제1항에 있어서,상기 이온전도체는 S-PI(sulfonated polyimide), S-PAES(sulfonated polyarylethersulfone), S-PEEK(sulfonated polyetheretherketone), 술포네이트 폴리벤즈이미다졸(sulfonated polybenzimidazole: S-PBI), 술포네이트 폴리술폰(sulfonated polysulfone: S-PSU), 술포네이트 폴리스티렌(sulfonated polystyrene: S-PS), 술포네이트 폴리포스파젠(sulfonated polyphosphazene) 또는 그들의 혼합물을 포함하는 고분자 전해질막.
- 제1항에 있어서,상기 고분자 전해질막은 기계적 강도가 10MPa이상인 것을 특징으로 하는 고분자 전해질막.
- 전구체(precusor)를 방사용매에 녹여 방사용액을 제조하는 공정;상기 방사용액을 전기방사하여 평균 직경이 0.005 내지 5 ㎛인 나노 섬유로 이루어진 다공성 나노 웹을 제조하는 공정;상기 다공성 나노 웹이 NMP, DMF, DMA, 또는 DMSO의 유기용매에 비용해성이 되도록 상기 다공성 나노 웹을 후처리하는 공정;상기 유기용매에 대해 용해성인 탄화수소계 물질을 포함한 이온전도체를 상기 유기용매에 용해시켜 이온전도체 용액을 제조하는 공정; 및상기 후처리된 다공성 나노 웹의 기공 내에, 아래 식에 의해 측정된 상기 나노 웹의 두께 비율이 20% 이상이 되도록, 상기 이온전도체 용액을 충진한 후 상기 유기용매를 제거하는 공정을 포함하는 고분자 전해질막.나노 웹의 두께 비율 = [A/(B+C)]×100상기 A는 나노 웹의 평균 두께이고, 상기 B는 상부 이온전도체의 평균 두께이며, 상기 C는 하부 이온전도체의 평균 두께이다.
- 제10항에 있어서,상기 전구체는 0.5 중량% 이하의 수분을 포함하는 고분자 전해질막의 제조방법.
- 제10항에 있어서,상기 후처리하는 공정은 열처리 공정 또는 화학적 처리 공정을 포함하는 고분자 전해질막의 제조방법.
- 제10항에 있어서,상기 다공성 나노 웹은 폴리이미드(polyimide) 또는 폴리벤즈옥사졸(polybenzoxazole)을 포함하는 고분자 전해질막의 제조방법.
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DE112010003385T DE112010003385T5 (de) | 2009-08-25 | 2010-08-25 | Polymer-Elektrolyt-Membran für eine Brennstoffzelle und Verfahren für derenHerstellung |
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US9136034B2 (en) | 2015-09-15 |
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