WO2008143362A1 - 固体高分子電解質、その製造方法、及び固体高分子型燃料電池 - Google Patents
固体高分子電解質、その製造方法、及び固体高分子型燃料電池 Download PDFInfo
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- WO2008143362A1 WO2008143362A1 PCT/JP2008/059854 JP2008059854W WO2008143362A1 WO 2008143362 A1 WO2008143362 A1 WO 2008143362A1 JP 2008059854 W JP2008059854 W JP 2008059854W WO 2008143362 A1 WO2008143362 A1 WO 2008143362A1
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- solid polymer
- polymer electrolyte
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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
- H01M8/1037—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes
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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
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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
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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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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- 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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a solid polymer electrolyte excellent in ion conductivity, and more particularly, to a solid polymer electrolyte used for a fuel cell, water electrolysis, salt electrolysis, oxygen concentrator, humidity sensor, gas sensor, and the like, and It relates to a manufacturing method.
- Ion conductivity Ion conductivity
- the present invention relates to a solid polymer electrolyte membrane excellent in power generation and a polymer electrolyte fuel cell excellent in power generation performance.
- a solid polymer electrolyte is known as a proton conducting electrolyte.
- This solid polymer electrolyte has an electrolyte group in the bond chain of the solid polymer material, and this electrolyte group is firmly bonded to a specific ion or selectively transmits a cation or an anion. Therefore, it is formed into particles, fibers, or membranes, and is used for various purposes such as electrodeposition, diffusion dialysis, and battery membranes.
- a solid polymer electrolyte membrane obtained by forming a solid polymer electrolyte into a membrane is used for salt electrolysis, solid polymer fuel cells, and the like.
- polymer electrolyte fuel cells are attracting attention as a clean and highly efficient power source because they have high energy conversion efficiency and emit almost no harmful substances, and have been actively researched in recent years. is there.
- solid polymer electrolyte membrane examples include a fluorine-containing electrolyte membrane, a polysiloxane electrolyte membrane, and a hydrocarbon electrolyte membrane.
- the fluorine-containing electrolyte membrane includes a type having a sulfonic acid group or a carboxylic acid group as an electrolyte group.
- a sulfonic acid group is provided as an electrolyte group.
- Fluorine-containing sulfonic acid membranes are generally used. Examples of such membranes include naphthion (registered trademark, DuPont) membrane, Flemion (registered trademark, Asahi Glass) membrane, and Aciplex (registered trademark, Asahi Kasei) membrane.
- the represented membrane is widely used.
- the structure of this type of fluorinated sulfonic acid film is maintained due to the crystallinity of the perfluoroalkylene chain, but because it is a non-crosslinked structure, the electrolyte group in the side chain is free. The degree is great. For this reason, in the ionized state, a strongly hydrophobic main chain portion and a hydrophilic electrolyte group coexist, and the electrolyte group associates with water molecules in the fluorocarbon matrix to form a water cluster.
- the water cluster has a structure in which spherical clusters (holes) of about several nanometers are connected by narrow channels (bottom necks) of about 1 nm.
- ion exchange groups which are hydrophilic groups, and water molecules associate to form water clusters.
- Proton conductivity can be expressed by protons moving in the water (cluster water) stored in the water cluster while diffusing.
- an electrolyte membrane having high ionic conductivity is desired in order to reduce the electric resistance during power generation as much as possible.
- the ion conductivity of the membrane greatly depends on the number of ion exchange groups, and fluorine-based ion exchange resin membranes having a dry weight (EW) per equivalent of about 9500 to 1200 are usually used. . Fluorine ion exchange resin membranes with an EW of less than 9500 show greater ionic conductivity, but are more likely to dissolve in water or hot water and have a major problem of poor durability when used in fuel cell applications. there were.
- Japanese Patent Application Laid-Open No. 2 0 0 2-3 5 2 8 19 discloses a low EW fluorine ion exchange resin membrane that can be used in a fuel cell.
- the dry weight (EW) per equivalent of ion-exchange group is 2500 or more and 9400 or less, and the weight reduction due to boiling in water for 8 hours is 5 wt on the basis of the dry weight before boiling.
- Fluorine ion-exchange resin membranes that are less than or equal to% are disclosed.
- the ion exchange resin membrane disclosed in Japanese Patent Laid-Open No. 2 0 3-5 2 8 1 9 is a ionic conductive membrane made of a conventional perfluorosulfonic acid electrolyte, although EW is slightly small. It is used under humidified conditions, and it was difficult to raise the operating temperature to 100 ° C or higher. Moreover, EW is 2 5 0 or more and 9 4 0 or less. In fact, only 614 with EW was produced.
- the present inventors have a small EW value to replace the conventional perfluorosulfonic acid electrolyte, excellent proton conductivity, excellent strength, thermal stability even under non-humidified conditions or low moisture.
- Invented a polymer electrolyte having a main chain skeleton.
- Japanese Patent Application Laid-Open No. 2006-1 14277 presented a proton conductive material having a dry weight (EW) per equivalent of ion-exchange group of 250 or less, preferably EW of 200 or less. Specifically, it is a proton conducting material with the basic structure of
- An object of the present invention is to further improve the ionic conductivity of a solid polymer electrolyte.
- the current electrolyte membrane material Nafion (registered trademark) exhibits high proton conductivity in a high humidity atmosphere, but low proton conductivity in a low humidity atmosphere.
- Reason J Until there is a hole that inhibits the flow of protons in part of the “water cluster structure” that is the path for protons to pass through, the amount of protons that diffuse in vain increases It is to do.
- the present inventor has reached the present invention by discovering that the ion conductivity in the electrolyte membrane can be improved by paying attention to the water cluster fabrication in the electrolyte membrane and controlling the structure.
- the present invention is an invention of a solid polymer electrolyte having a water cluster structure composed of a hydrophilic group in the solid polymer electrolyte and occluded water, and is calculated by a dissipative particle dynamics method.
- the difference in water cluster structure which is the difference between the diameter of the hole in the water cluster structure and the diameter of the bottleneck, is 15.4 X 0. 072 nm or less.
- Figure 1 schematically shows a cross-section of a water cluster structure composed of hydrophilic groups and occluded water in the solid polymer electrolyte.
- One water cluster structure has a spherically expanded hole and a narrow bottleneck. Protons move without diffusing at the bottleneck, while protons diffuse 3 ⁇ at the hole, resulting in slower movement in the desired direction.
- the diameter of the hole in this water cluster structure And the difference between the diameter of the bottleneck portion.
- the solid polymer electrolyte of the present invention preferably has an average water cluster diameter defined below of the water cluster structure of 12.7 X 0 .07 2 nm or less.
- Average water cluster diameter ⁇ n R / ⁇ n
- the polymer electrolyte characterized by the water cluster structure of the present invention is a conventionally known fluorine-containing electrolyte, polysiloxane. System electrolytes, hydrocarbon electrolytes, etc. are applied, and a preferable molecular structure is searched by kinetically simulating the bond spacing and bond distribution of ion-exchange groups that are hydrophilic groups with respect to the main chain.
- a polymer electrolyte may be synthesized based on the molecular design.
- the molecular design of the present invention can be easily performed by utilizing the structure and synthesis method previously invented by the present inventors. Specifically, it is a solid polymer electrolyte having the following structural formula as a basic skeleton.
- the present invention provides hydrophilicity in the solid polymer electrolyte.
- the invention relates to a method for producing a solid polymer electrolyte having a water cluster structure composed of a group and occluded water, wherein the distance between side chains of side chains having ion exchange groups and dispersion of the ion exchange groups are adjusted.
- the difference in water cluster structure which is the difference between the diameter of the hole of the water cluster structure calculated by the dissipative particle dynamics method and the diameter of the bottle neck, is 15.4 X 0 .0 7 2 nm or less It is what.
- a monomer unit constituting the polymer electrolyte and having no side chain referred to as b component in this specification
- a monomer unit having a side chain having an ion-exchange group referred to as component a
- component a may be appropriately adjusted in the order of addition or addition amount during the polymer synthesis reaction.
- component b After the polymerization or polycondensation of component a is allowed to proceed for a certain period of time, component b is added and polymerized or polycondensed again.
- component a After the polymerization or polycondensation of component b is allowed to proceed for a certain period of time, component a is added and polymerized or polycondensed again.
- the polymerization or polycondensation is continued while adding the b or a component during the polymerization or polycondensation of the a or b component.
- Specific examples of the method for producing a solid polymer electrolyte of the present invention include a step of oxidizing a mercapto group of a mercaptoalkyl trialkoxysilane to form a sulfonic acid, a step of converting an alkoxy group of the trialkoxysilane alkylsulfonic acid into a hydroxyl group, A step of synthesizing component a in the step of polycondensation of hydroxysilane silane alkyl sulfonic acid, and synthesizing component a in the step of polycondensation of silane alkyl sulfonic acid hydroxide, wherein the alkoxy group of tetraalkoxy silane is converted to a hydroxyl group
- a method for producing a solid polymer electrolyte having the above structural formula as a basic skeleton by suitably adding the component b obtained in (1) and polycondensing these monomeric compounds is preferably exemplified.
- a sol-gel method is preferably exemplified as the step of condensing these monomer compounds.
- the present invention is a solid polymer electrolyte membrane comprising the above solid polymer electrolyte.
- the present invention is a polymer electrolyte fuel cell having the solid polymer electrolyte.
- the difference in structure of the water cluster which is the difference between the diameter of the hole of the water cluster structure constituted by the hydrophilic group in the solid polymer electrolyte and the occluded water and the diameter of the bottleneck, is specified.
- a solid polymer electrolyte excellent in ion conductivity can be provided.
- this polymer electrolyte when used as a polymer electrolyte membrane of a polymer electrolyte fuel cell, a polymer electrolyte fuel cell having excellent proton conductivity and excellent power generation performance even in a low humidified state can be obtained. it can.
- Figure 1 schematically shows a cross-section of a water cluster structure composed of hydrophilic groups in the solid polymer electrolyte and occluded water.
- Figure 2 shows an example of a molecular structure model of a polyelectrolyte.
- Figure 3 shows the size (diameter) of the water cluster structure in the molecular structure models 1 to 3 calculated by simulation using the dissipative particle dynamics method.
- FIG. 4 shows a synthetic scheme of a silicone polymer having three kinds of molecular structures shown in FIG.
- Figure 5 shows the M S D (mean square displacement) versus time for molecular structure models 1, 2 and 3.
- Figure 6 schematically shows the effect of water cluster structure on the diffusion of water molecules.
- Figure 7 shows the correlation between the average water cluster diameter of the water cluster structure and the diffusion coefficient.
- Figure 8 shows the correlation between the difference in water cluster structure and the diffusion coefficient.
- Figure 2 shows an example of a molecular structure model of a polyelectrolyte.
- the ion exchange group density (EW) is the same polymer electrolyte, but the molecular structure (the distance between the side chains having ion exchange groups and the ion exchange with the main chain). The distribution of side chains with groups) may be different.
- Figure 3 shows the “water cluster structure” inside each electrolyte membrane for molecular structure models 1 to 3.
- the size (diameter) of the particles is calculated by simulation using the dissipative particle dynamics method. As a result, it was found that a diameter of several nanometers and a diameter of several tens of nanometers coexist.
- the polymer electrolyte membrane has a structure with a small diameter (hereinafter referred to as the bottle neck) and a structure with a large diameter (hereinafter referred to as the hole), as shown in Fig. 1 above. It is thought to be represented in the figure. From Fig. 1 to Fig. 3, it can be seen that the distribution of pores changes according to molecular structure models 1 to 3.
- the solid polymer electrolyte used in the present invention refers to a polymer having an electrolyte group or a precursor thereof.
- the polymer include a fluorinated polymer in which the entire polymer skeleton is fluorinated, and a part of the polymer skeleton is fluorinated (for example, 1 CF 2 —, 1 CHF—, 1 CFC 1 Fluorine-hydrocarbon polymers having a bond such as —, hydrocarbon polymers not containing fluorine in the high molecular skeleton, and silicone polymers having a silicone skeleton.
- a tetrafluoroethylene polymer a tetrafluoroethylene perfluoroalkyl butyl ether copolymer, a tetrafluoroethylene monohexafluoro Propylene copolymer, Tetrafluoroethylene monohexafluoropropylene monoperfluororeoleolanorequinolino vinylene tenole copolymer, Tetrafluoroethylene monotrifluorostyrene copolymer, Tetrafluoro Ethylene monotrifluorostyrene one perfluoro anoalkyl butyl ether copolymer, hexafluoro propylene mono trifluoro styrene copolymer, hexafluoro oral propylene mono trifluoro styrene one perfluoroalkyl vinyl ether
- copolymers examples thereof include copolymers.
- Fluorine 'Hydrocarbon-based polymers include polyvinylidene fluoride, polystyrene-graft-ethylenetetrafluoroethylene copolymer, polystyrene-graft-polytetrafluoroethylene, polystyrene-graft-polyvinylidene fluoride, polystyrene-one Examples include graft-hexafluoropropylene tetrafluoroethylene copolymer, polystyrene-graft-ethylene-hexafluoropropylene copolymer, and the like.
- Hydrocarbon polymers include polyetheretherketone, polyetherketone, polysulfone, polyethersulfone, polyimide, polyamide, polyamideimide, polyetherimide, polyphenylene ether, polyphenylene ether, polyphenylene ether, polyphenylene ether, Examples include carbonate, polyester, and polyacetal. Particularly preferred are those containing aromatics in the skeleton, and more preferred are wholly aromatic ones.
- General-purpose resins such as polyethylene, polypropylene, polystyrene, and acrylic resins may be used.
- the electrolyte group of the solid polymer electrolyte may be a functional group capable of proton conduction, and specifically, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, and the like are preferable.
- the precursor of the electrolyte group may be a functional group capable of conducting a proton by derivatization by chemical reaction (for example, hydrolysis).
- the precursor of the sulfonic acid group, phosphonic acid Preferred are a precursor of a group, a precursor of a carboxylic acid group, and the like.
- Particularly preferred are metal ions such as fluoro and sodium.
- the solid polymer electrolyte may contain one type of electrolyte group or its precursor, or may contain two or more types.
- Examples of such a solid polymer electrolyte include a fluorine-containing electrolyte having an electrolyte group or its precursor on a fluorine-containing polymer, and a fluorine having an electrolyte group or its precursor on a fluorine / hydrocarbon polymer.
- Examples thereof include hydrocarbon electrolytes and silicone electrolytes, which are electrolytes based on hydrocarbons, electrolytes based on hydrocarbon polymers, or precursors thereof. This Of these, polymer electrolytes that can be easily designed and synthesized are preferred.
- This silicone electrolyte is produced from a specific silane material by a sol-gel method. That is, a silicon-based electrolyte having the following structural formula as a basic skeleton is produced by a sol-gel method using mercaptoalkyltrialkoxysilane and optionally tetraalkoxysilane as starting materials.
- the silicone electrolyte is produced by the step of condensing the nomer compound.
- R 1 and R 3 are alkyl groups, and R 2 is an alkylene group.
- Hydrogen peroxide and t-butanol used in the step of oxidizing the mercapto group to form sulfonic acid are easily evaporated and removed from the reaction system.
- the sulfonic acid group (_S0 3 H) generated in the process of forming a sulfonic acid is used in the process of converting the alkoxy group to a hydroxyl group.
- the present invention is a very rational production method in which reaction by-products and impurities are not generated.
- the mercaptoalkyltrialkoxysilane is preferably 3-mercaptopropyl trimethoxysilane (Me PTMS), and the tetraalkoxysilane is preferably tetramethoxysilane (TMOS).
- Me PTMS 3-mercaptopropyl trimethoxysilane
- TMOS tetramethoxysilane
- the solid polymer electrolyte is preferably in the form of a membrane, but is not particularly limited, and various shapes can be selected according to the application.
- the solid polymer electrolyte of the present invention When used, for example, as a solid polymer electrolyte membrane of a solid polymer fuel cell, it has superior conductivity in a high temperature and low humidity environment as compared with a conventional electrolyte membrane. Operation at high temperature and low humidity is possible, improving battery performance.
- the solid polymer electrolyte we synthesized a silicone polymer with the three molecular structures shown in Fig. 2. That is, by synthesizing the a component and the b component and adjusting the timing of adding the b component in the synthesis scheme shown in FIG.
- the polymer electrolytes shown in the molecular structure models 1 to 3 were synthesized.
- the ion exchange group density (EW) is the same polyelectrolyte, but the molecular structure (distance of side chains having ion exchange groups and distribution of side chains having ion exchange groups with respect to the main chain) ) Is a different electrolyte.
- a polymer electrolyte To synthesize the polymer electrolytes shown in the molecular structure models 1 to 3 as a method of adjusting the distance between the side chains of the side chains having ion exchange groups and the dispersion of the ion exchange groups, a polymer electrolyte must be constructed.
- the molecular structure model 1 is obtained by uniformly mixing the a component and the b component from the beginning and reacting them in a homogeneous system.
- Molecular structure models 2 and 3 are obtained by allowing polycondensation of component a to proceed for a fixed time, adding component b, reacting in a heterogeneous dispersion system, and performing polycondensation again.
- the ion exchange group density (EW) is the same polymer electrolyte, but the molecular structure (the distance between the side chains having ion exchange groups, and It is possible to produce electrolytes that differ only in the distribution of side chains having ion exchange groups with respect to the main chain.
- Figure 5 shows the MSD (mean square displacement) over time for molecular structure models 1, 2 and 3.
- the slope at this time shows the diffusion coefficient D of water, and the diffusion coefficient improves in the order of molecular structure model 3> molecular structure model 2> molecular structure model 1.
- the reason why the diffusion coefficient changes depending on the molecular structure is the presence of pores trapping water molecules in the water cluster structure.
- Figure 6 schematically shows the effect of the water cluster structure on the diffusion of water molecules. As shown in Fig. 6, it can be seen that the proton distribution performance improves as the distribution of pores in the water cluster structure decreases.
- Figure 7 shows the correlation between the average water cluster diameter of the water cluster structure and the diffusion coefficient.
- the results in Fig. 7 clearly show the tendency for the diffusion coefficient to improve as the average water cluster diameter (average size) of the water cluster structure decreases.
- the smaller the average size of the water cluster structure the better the proton conduction performance of the electrolyte membrane.
- the desired diffusion coefficient is exhibited when the average water cluster diameter defined below in the water cluster structure is 12.7 X 0.072 nm or less.
- Average diameter of water cluster ⁇ n R Z ⁇ n
- the size of the hole is calculated by the following formula.
- Average size (bottleneck size + hole size) / 2
- Figure 8 shows the correlation between the difference in water cluster structure and the diffusion coefficient. From the results shown in FIG. 8, the difference in the water cluster structure, which is the difference between the diameter of the hole in the water cluster structure and the diameter of the bottleneck, is less than 15.4 X 0.0 7 2 nm. Can be seen.
- a silicone-based polymer electrolyte was used because of the ease of molecular design, but similar results can be obtained using other solid polymer electrolytes such as Naphion (trade name). Industrial applicability
- a solid polymer electrolyte having excellent ion conductivity can be provided.
- this solid polymer electrolyte is used as a solid polymer electrolyte membrane of a solid polymer fuel cell, a solid polymer fuel cell having excellent proton conductivity and excellent power generation performance even in a low humidified state can be obtained. it can. This will contribute to the practical application and diffusion of fuel cells.
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Abstract
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Priority Applications (3)
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US12/600,845 US20100167167A1 (en) | 2007-05-22 | 2008-05-22 | Solid polymer electrolyte, method for production thereof, and solid polymer fuel cell |
CN200880014118A CN101675549A (zh) | 2007-05-22 | 2008-05-22 | 固体高分子电解质、其制造方法和固体高分子型燃料电池 |
DE112008001332T DE112008001332T5 (de) | 2007-05-22 | 2008-05-22 | Festpolymer-Elektrolyt, Verfahren zum Herstellen desselben und Festpolymer-Brennstoffzelle |
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JP2007135868A JP2008293709A (ja) | 2007-05-22 | 2007-05-22 | 固体高分子電解質、その製造方法、及び固体高分子型燃料電池 |
JP2007-135868 | 2007-05-22 |
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WO2008143362A1 true WO2008143362A1 (ja) | 2008-11-27 |
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JP (1) | JP2008293709A (ja) |
CN (1) | CN101675549A (ja) |
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JP2009238515A (ja) * | 2008-03-26 | 2009-10-15 | Fujifilm Corp | 高分子電解質膜、膜電極接合体および燃料電池 |
US20110039951A1 (en) * | 2009-03-20 | 2011-02-17 | Hydro Electron Ventures | Water clusters confined in nano-environments |
DE102012016815A1 (de) * | 2012-08-24 | 2013-10-24 | Fraunhofer-Institut für Angewandte Polymerforschung IAP | Elektrolyt, elektrochemischer Sensor und Verwendung von partikulären Bestandteilen |
EP2997617B1 (en) * | 2013-05-16 | 2018-10-10 | United Technologies Corporation | Flow battery with hydrated ion-exchange membrane having maximum water domain cluster sizes |
WO2019088298A1 (ja) * | 2017-11-06 | 2019-05-09 | Agc株式会社 | レドックスフロー電池に好適なイオン交換膜 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004112177A1 (ja) * | 2003-06-13 | 2004-12-23 | Sekisui Chemical Co., Ltd. | プロトン伝導性膜、その製造方法およびこれを用いた燃料電池 |
JP2006114277A (ja) * | 2004-10-13 | 2006-04-27 | Toyota Motor Corp | プロトン伝導材料、固体高分子電解質膜、及び燃料電池 |
JP2007138028A (ja) * | 2005-11-18 | 2007-06-07 | Sekisui Chem Co Ltd | プロトン伝導性膜の製造方法、プロトン伝導性膜及び燃料電池 |
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JP2006114277A (ja) * | 2004-10-13 | 2006-04-27 | Toyota Motor Corp | プロトン伝導材料、固体高分子電解質膜、及び燃料電池 |
JP2007138028A (ja) * | 2005-11-18 | 2007-06-07 | Sekisui Chem Co Ltd | プロトン伝導性膜の製造方法、プロトン伝導性膜及び燃料電池 |
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