WO2004097850A1 - プロトン伝導性膜、その製造方法およびそのプロトン伝導性膜を用いた燃料電池 - Google Patents
プロトン伝導性膜、その製造方法およびそのプロトン伝導性膜を用いた燃料電池 Download PDFInfo
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- WO2004097850A1 WO2004097850A1 PCT/JP2004/005885 JP2004005885W WO2004097850A1 WO 2004097850 A1 WO2004097850 A1 WO 2004097850A1 JP 2004005885 W JP2004005885 W JP 2004005885W WO 2004097850 A1 WO2004097850 A1 WO 2004097850A1
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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
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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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
- C08J5/18—Manufacture of films or sheets
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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
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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
- H01M8/02—Details
- H01M8/0289—Means for holding the 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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- 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
- H01M8/1074—Sol-gel processes
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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 proton conductive membrane, a method for producing the same, and a fuel cell using the same. More specifically, the present invention is excellent in heat resistance, durability, dimensional stability, fuel barrier properties, etc.
- the present invention relates to a proton conductive membrane exhibiting proton conductivity, a method for producing the same, and a fuel cell capable of operating at a high temperature or directly supplying a fuel (eg, methanol or the like) by using the same.
- Fuel cells are generally classified into several types depending on the type of electrolyte. Among them, polymer electrolyte fuel cells (hereinafter sometimes abbreviated as PEFCs) are compared with all other types. It is small and high power, and is considered to be the mainstay of next generation as a power source for small-scale on-site type, mobile (for example, vehicle power source), and portable power sources. Is being done.
- PEFCs polymer electrolyte fuel cells
- PEFCs typically use hydrogen as a fuel. Hydrogen is decomposed into protons (hydrogen ions) and electrons by a catalyst installed on the anode side of the PEFC. Of these, electrons are supplied externally, used as electricity, and circulated to the power source side of the PEFC. On the other hand, protons are supplied to the proton conductive membrane (electrolyte membrane) and move to the force sword side through the proton conductive membrane. On the force side, protons, circulated electrons, and oxygen introduced externally are combined by the catalyst to produce water. In other words, PEFC alone is a very clean energy source that extracts electricity when making water from hydrogen and oxygen. Normally, hydrogen is used as fuel for fuel cells, but alcohol, ether, hydrocarbons, etc.
- Fuel cells that use fuel directly are also under active consideration.
- a typical example is a direct methanol fuel cell (hereinafter sometimes abbreviated as DMFC) using methanol (usually used as an aqueous solution) as a fuel.
- the proton conductive membrane has a role of transmitting protons generated at the anode to the force side. As described above, this proton transfer occurs in concert with the flow of electrons. That is, in order to obtain high output (that is, high current density) in PEFC, it is necessary to conduct a sufficient amount of proton conduction at high speed. Therefore, it is not an exaggeration to say that the performance of the proton conductive membrane is a key material that determines the performance of PEFC.
- the proton conductive membrane not only conducts protons, but also functions as an insulating film that electrically insulates the anode and the cathode, and a fuel that prevents fuel supplied to the anode from leaking to the force side. Also has a role as a barrier film.
- the main proton conductive membranes used in PEFCs are fluororesin-based membranes having perfluoroalkylene as the main skeleton and partially having a sulfonate group at the end of the perfluorovinylether side chain.
- a sulfonated fluororesin membrane include a Nafion (registered trademark) membrane (see Du Pont, US Patent No. 4,330,654) and a Dow membrane (Dow Ch).
- these fluororesin-based membranes have a glass transition temperature (Tg) around 130 ° C under the wet condition in which the fuel cell is used. From around this temperature, the so-called creep phenomenon occurs. As a result, the proton conduction structure in the membrane changes, and stable proton conduction performance cannot be exhibited. In addition, the membrane transforms into a swollen form, becomes jelly-like, and becomes very fragile, leading to failure of the fuel cell. For the above reasons, the maximum temperature that can be used stably for a long time at present is usually 80 ° C.
- Fuel cells use chemical reactions in their principle, so operating at high temperatures is more energy efficient. In other words, considering the same output, a device that can operate at high temperature can be smaller and lighter. When operated at high temperatures, the waste heat can also be used, so that so-called cogeneration (combined heat and power) is possible, and the total energy efficiency is dramatically improved. Therefore, it is considered that the operating temperature of the fuel cell should be high to some extent, usually 100 ° C. or more, particularly preferably 120 ° C. or more.
- the catalyst used on the anode side may lose its activity due to fuel impurities (for example, carbon monoxide).
- catalyst poisoning is a major issue that affects the life of PEFC. It is known that this catalyst poisoning can be avoided if the fuel cell can be operated at a high temperature. From this point, it can be said that it is preferable to operate the fuel cell at a higher temperature. Furthermore, when operation at higher temperatures becomes possible, the catalyst itself does not need to use pure products of precious metals such as platinum, which are conventionally used, and it becomes possible to use alloys with various metals. This is also very advantageous from the point of view of resources and resources.
- the heat resistance of the proton conductive membrane is up to 80 ° C as described above, so the operating temperature It is currently regulated up to 80 ° C.
- the reaction that occurs during the operation of the fuel cell is an exothermic reaction, and when the fuel cell is operated, the temperature in the PEFC rises spontaneously.
- Nafion which is a typical proton conductive membrane currently used, has only heat resistance up to about 80 ° C, so it is necessary to cool PEFC so that it does not exceed 80 ° C. is there. Cooling is usually carried out by a water cooling method, and such cooling measures are introduced into the separator part of the PEFC. By taking such cooling measures, the PEFC becomes larger and heavier as a whole, making full use of the inherent features of PEFC such as small size and light weight. Can not.
- the operating limit temperature is 80 ° C
- effective cooling is difficult with the simplest water cooling method as the cooling means. If operation at 100 ° C or higher is possible, cooling can be effectively performed as the heat of evaporation of water, and the amount of water used for cooling can be dramatically reduced by refluxing the water. Miniaturization and weight reduction can be achieved.
- comparing the case of controlling the temperature at 80 ° C with the case of controlling the temperature at 100 ° C or more can greatly reduce the radiator and cooling water capacity.
- a PEFC that can operate at or above ° C, that is, a proton conductive membrane that has heat resistance of at least 100 ° C.
- PEFC high-temperature operation of PEFC, that is, high-temperature heat resistance of proton conductive film is desired in various aspects such as power generation efficiency, cogeneration efficiency, cost resources, and cooling efficiency. Nevertheless, there is no proton conductive membrane that has both sufficient proton conductivity and heat resistance.
- Typical examples thereof include heat-resistant aromatic high-molecular materials that can replace conventional fluorine-based films, such as polybenzimidazole (see JP-A-9-110982) and polyether. Sulfone (see JP-A-10-21943 and JP-A-10-45913), polyetheretherketone (see JP-A-9-87510) and the like.
- aromatic polymer materials have the advantage that there is little structural change at high temperatures.On the other hand, many aromatic polymers directly introduce sulfonic acid groups and carboxylic acid groups into the aromatics. , There is a high possibility that remarkable desulfonation and decarboxylation occur, which is not preferable as a high-temperature working membrane.
- these aromatic polymer materials do not have an ion channel structure (described later) unlike fluororesin-based membranes.
- an acid group is required to obtain sufficient proton conductivity. It is necessary to introduce a large number of them, and there is a problem that heat resistance and hot water resistance decrease, and in some cases, they are dissolved by hot water. Furthermore, the presence of water tends to cause the entire membrane to swell strongly like the fluororesin membrane.
- inorganic materials have been proposed as proton conductive materials.
- Minami et al. Obtained a proton conductive inorganic material by adding various acids to a hydrolyzable silyl compound (Solid State Ionics, vol. 74, p. 105). , 1994.).
- these inorganic materials exhibit stable proton conductivity even at high temperatures, but when used as a thin film, they have a problem that they are easily broken, making it difficult to handle and produce a membrane-electrode assembly.
- Japanese Patent Application Laid-Open No. 1092/444 (published in US Pat. No. 6,242,135) has continuous pores, and the inside surfaces of the pores are covered with a metal oxide.
- a composite in which a solid electrolyte is contained in the pores of a stretched porous polytetrafluoroethylene molded article has been reported.
- the production process of such a complex is complicated and economically unfavorable, and furthermore, the physical properties of the metal oxide conductive agent and the molded body support are greatly different. Adhesion and stability as a film are considered to be insufficient.
- examples are given in which the metal oxide is silica gel. However, silica gel has poor flexibility and is considered to be an obstacle to subsequent processing.
- Japanese Patent Application Laid-Open No. 2002-3598979 discloses a metaphenylene isophthala A polymer solid electrolyte composite membrane composed of a porous polymer having a large number of uniform micropores on its surface and inside, and a polymer solid electrolyte substance contained in the pores, has been reported. Although such a film has the advantage of increasing the mechanical strength, meta-phenylene isophthalamide-based polymer has insufficient resistance to oxidation and strong acid under high temperature and high humidity conditions. There is a possibility of causing breakage.
- Japanese Patent Application Laid-Open No. 200-83636 discloses a proton conductive polymer having one end bonded to the inner surface of a pore of a porous substrate having swelling resistance to an organic solvent and water.
- An electrolyte membrane has been reported in which a second proton conductive polymer, the same or different from the first polymer, is filled in the pores after the formation of the polymer.
- any one of ceramic, glass, and alumina or a composite material thereof, or polytetrafluoroethylene or polyimide is proposed.
- inorganic materials such as ceramics, glass, and alumina do not show a great effect in terms of film strengthening even when used as a support because the substrate itself is a brittle material.
- a heat-resistant polymer such as polytetrafluoroethylene or polyimide
- it is difficult to form a bond with a chemically inert material such as polytetrafluoroethylene, and it is difficult to form a bond.
- bonds will be easily dissociated, making it difficult to obtain a stable membrane.
- heat-resistant polymers such as polyimide have problems in oxidation stability and acid resistance, and it is also difficult to form a stable film.
- organic polymer electrolytes have a high affinity for protic solvents such as methanol, so it is unavoidable that they dissolve and swell, dissolving them, which is a major challenge for DMFC development. I have. Inorganic electrolytes are also being considered in order to prevent such penetration, swelling and dissolution, but as mentioned above, inorganic electrolytes are brittle and are difficult to install directly in fuel cells.
- An object of the present invention is to solve the problems of conventional polymer electrolyte fuel cells by providing excellent heat resistance, durability, dimensional stability, fuel barrier properties, etc., and excellent proton conductivity even at high temperatures.
- Proton conductive membrane shown, its manufacturing method and its use can respond to high-temperature operation or direct fuel (for example, methanol) supply It is to provide a fuel cell.
- Another object of the present invention is to provide a method for producing a proton conductive membrane, which can economically and efficiently produce the proton conductive membrane of the present invention.
- Still another object of the present invention is to provide a fuel cell that can operate stably at a high temperature by using the proton conductive membrane of the present invention.
- the present inventors have conducted intensive studies and, as a result, have examined various electrolyte membrane materials.As a result, they have a crosslinked structure having a specific organic-inorganic composite structure as an essential component constituting the membrane.
- a proton conductive structure (j8) into a support (h) having a continuous pore structure, a proton conductive membrane with excellent durability, dimensional stability, fuel barrier properties, etc.
- the present invention was achieved. That is, according to the first aspect of the present invention, an organic-inorganic material having a cross-linked structure formed by a metal-oxygen bond, and having a continuous pore structure in which pores formed inside by the bridge structure are continuously connected.
- a proton conductive membrane is provided, which is obtained by filling a support made of a composite structure ( ⁇ ) with a proton conductive structure () containing an acid-containing structure containing an acid group.
- a proton conductive membrane characterized by being in the range of 1: 25.
- the organic-inorganic composite structure ( ⁇ ) is provided in the proton conductive membrane.
- a proton conducting film wherein the metal atoms in the proton conductive film are silicon atoms.
- the porosity of the continuous pore structure is 2095% by volume in the support made of the organic-inorganic composite structure ( ⁇ ).
- a proton conducting membrane is provided.
- the proton conductive membrane wherein the pore diameter of the pores is 0.011 Om in the proton conductive membrane.
- ⁇ is a silicon atom
- X is a 0-bond or ⁇ group involved in crosslinking
- R 1 is a carbon atom-containing molecular group having 150 carbon atoms
- R 2 is a methyl, ethyl, propyl or phenyl group
- nl 112 is 01 or 2 and at least ⁇ 1 ⁇ 2
- a proton conductive membrane is provided.
- the number of groups X involved in crosslinking of the organic-inorganic composite structure ( ⁇ ) represented by the chemical formula (1) is represented by the following formula ( II); a: 2.9 ⁇ a ⁇ 3.5
- n 1 i, n 2 1 is an organic-inorganic composite (shed) i, represents n 1, n 2 in the formula (1), ⁇ , 1 or 2, and at least the n 1 1, n 2 1 One is 1 or 2, and mi represents a mole fraction).
- a 3.0.
- the proton conductive structure (] 3) has a crosslinked structure of metal monooxygen atoms, and is represented by the following formula (3).
- a proton-conductive film characterized by including the acid group-containing structure (A).
- M is a silicon atom
- X is a single O-bond or OH group involved in crosslinking
- R 3 is a molecular chain group having at least one acid group
- R 4 is a methyl, ethyl, propyl or phenyl group
- m is 0, 1 or 2.
- R 3 has a structure represented by the following formula (12).
- the proton conductive structure ( ⁇ ) I is represented by the formula (3).
- the metal-oxygen bond structure (B) bonded to the structure of the formula (3) by a metal-oxygen bond is included.
- a featured proton conductive membrane is provided.
- the proton conductive membrane includes a metal-oxygen bonding structure (B) 1S and an organic-inorganic composite structure (2) represented by the following formula: A proton conductive membrane is provided.
- M is a silicon atom
- X is a single O-bond or OH group involved in the crosslinking
- R 1 is a carbon atom-containing molecular chain group having 1 to 50 carbon atoms
- R 2 is a methyl, ethyl, propyl or phenyl group
- nl and 112 are 0, 1 or 2
- the metal-oxygen bond structure (B) includes a structure represented by the following formula (6). Is done.
- M is a metal atom
- X is a single O-bond or an OH group involved in crosslinking
- R 2 is a methyl, ethyl, propyl or phenyl group
- m is 0, 1
- M is a metal atom
- X is a single O-bond or an OH group involved in crosslinking
- R 2 is a methyl, ethyl, propyl or phenyl group
- m is 0, 1
- M is a metal atom
- X is a single O-bond or an OH group involved in crosslinking
- R 2 is a methyl, ethyl, propyl or phenyl group
- m is 0, 1
- a tetrafunctional metal such as tetraalkoxysilane
- a tetrafunctional metal is effective.
- an organic-inorganic composite (a step of preparing a mixture containing an organic-inorganic composite crosslinkable compound (c) having a crosslinkable silyl group at its terminal and a carbon atom covalently bonded thereto, and a step of forming a film of the mixture. And a step of hydrolyzing and / or condensing a crosslinkable silyl group contained in the formed mixture.
- the organic-inorganic composite crosslinkable compound (C) is represented by the following formula (4):
- R 1 is a carbon atom-containing molecular chain group having 1 to 50 carbon atoms
- R 2 is a methyl, ethyl, propyl or phenyl group; 1 is ⁇ 1, OH, OCH 3 , OC 2 H C , OC 3 H 7 , OC 4 H 9 , OC 6 H 5 , OCOCH 3 And nl, 2 represents 0, 1 or 2, and at least one of nl and n2 represents 1 or 2.
- the present invention provides a method for producing a proton conductive membrane characterized by the following. According to the eighteenth aspect of the present invention, in the method for producing a proton conductive membrane, the number of hydrolyzable groups of the organic-inorganic composite crosslinkable compound (C) represented by the formula (4) is as follows: Formula (II);
- P is an organic-inorganic composite crosslinkable compound type an integer of 1 or more to a number of (C), also i represents an integer of 1 to P, n 1 1, n 2 1 is , Organic-inorganic composite frame Bridges compound in (C) i, represents nl, the n 2 in the formula (4), 0, 1 or 2, and at least one of n 1 1, n 2 1 is 1 or 2, mi is (Indicating a mole fraction) is provided.
- a 3.0. Is done.
- the method for producing a proton conductive membrane in the method for producing a proton conductive membrane, 0.5 to 1.5 equivalents of the crosslinkable silyl group in the organic-inorganic composite crosslinkable compound (C) may be used.
- a method for producing a proton conductive membrane further comprising a step of adding a catalyst by adjusting a catalyst amount so that water is present.
- in the method for producing a proton conductive membrane in hydrolyzing a crosslinkable silyl group in the organic-inorganic composite crosslinkable compound (C), prensted acid is used.
- a method for producing a proton conductive membrane which is used as a catalyst.
- the organic-inorganic composite crosslinkable compound (C) in the method for producing a proton conductive membrane, is replaced with the solid component (g) of the organic-inorganic composite crosslinkable compound (C). ), The method further comprises a step of mixing with a solvent in an amount of 0.5 to 1 Om 1 Zg.
- the organic-inorganic composite structure () in the method for producing a proton conductive film, contains an acid group-containing compound (D) containing at least a crosslinkable silyl group and an acid group.
- the acid group-containing compound (D) has a structure represented by the following formula (7).
- R 6 is any group of OH, OCH 3 , OC 2 H 5 , OC 3 H
- R 3 a molecular chain having at least one acid group
- R 4 a methyl, ethynole, propyl or phenyl group
- the acid group-containing compound (D) is represented by the following formula (8).
- the method includes a substance having a structure.
- R 3 is a molecular chain group having at least one acid group
- R 7 a group selected from the group consisting of H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9, and C 6 H 5 , and a branch partially forming one Si bond It may have a structure or an intramolecular cyclic structure.
- R 8 , RR 10 , R 11 R 0 , OH, OCH 3 s OC 2 H 5 , OC 3 H 7 , OC 4 H 9 , OC 6 H 5s CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , C 6 H 5 It may have an i-bonded branched structure or an intramolecular cyclic structure.
- n Integer from 1 to 50
- n and t may be used.
- R 3 is a structure represented by the following formula (12). A method for producing a proton conductive membrane is provided.
- the organic-inorganic composite structure (where the mixture to be filled in c) is A method for producing a proton conductive membrane comprising a crosslinkable compound (F) represented by the following formula (16) in addition to an acid group-containing compound (D) containing a crosslinkable silyl group and an acid group: Provided.
- R 5 OH, OCH 3 , OC 2 H 5 , OC 3 H 7 , OC 4 H 9 , OC 6 H 5 , Cl, any one of OCOCH 3 groups,
- R 2 a methyl, ethyl, propyl or phenyl group; m represents 0, 1 or 2)
- the organic-inorganic composite structure (wherein at least a crosslinkable silyl group and an acid precursor group convertible to an acid group are included in Q).
- a proton conductive material having an acid group inside the organic-inorganic composite structure ( ⁇ ) can be obtained.
- a method for producing a proton conductive film which is produced by a method including a step of forming a conductive structure ( ⁇ ). The method for producing a conductive film, wherein the acid group precursor is contained.
- Objects (E) are provided methods for producing the proton conducting membrane, characterized in that has a structure represented by the following formula (1 7) is provided.
- R 12 is any group of OH, OCH 3 , OC 2 H 5 , OC 3 H 7
- R 13 a molecular chain having at least one acid group precursor
- R 4 any group of methyl, ethyl, propyl or phenyl group; m: 0, 1 or 2)
- the group precursor-containing compound (E) includes a compound having a structure represented by the following chemical formula (13).
- R 13 is a molecular chain group having at least one acid group precursor
- R ′ a group selected from the group consisting of H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9, and C 6 H 5 , and a branch partially forming one Si bond It may have a structure or an intramolecular cyclic structure.
- n Integer from 1 to 50
- R has a structure represented by the following formula (15).
- n is an integer of 1 to 20.
- the proton-conductive membrane filled in the organic-inorganic composite structure ( ⁇ ) provides a method for producing a proton conductive membrane, comprising a crosslinking compound (F) represented by the following formula (14) in addition to the compound (E) containing the iK acid group precursor (E). You.
- the third fuel cell of the present invention comprises the above-mentioned proton conductive membrane of the present invention. It is a thing.
- the proton conductive membrane of the present invention is excellent in heat resistance, durability, dimensional stability, fuel barrier properties, flexibility and the like, and can be used well even at high temperatures.
- the operating temperature of the polymer electrolyte fuel cell which has received much attention, can be raised to 100 ° C or higher.
- the proton conductive membrane of the present invention is excellent in durability, dimensional stability, fuel barrier properties, flexibility, etc., and can be suitably used even in a direct fuel type fuel cell such as DMFC. It is expected to be used for a long period of time for equipment and the like.
- the method for producing a proton conductive membrane of the present invention makes it possible to economically and efficiently produce the proton conductive membrane of the present invention.
- the organic-inorganic composite structure ( ⁇ ) has the structure represented by the above formula (1), and therefore, has particularly improved adhesion and heat resistance with the proton conductive membrane (] 3), The acid resistance, oxidation resistance and swelling resistance are more remarkably improved.
- FIG. 1 is a diagram showing a voltage-current curve of a fuel cell using the proton conductive membrane of one example of the present invention
- FIG. 2 is a diagram showing a voltage-current curve of a fuel cell using a proton conductive membrane of another example of the present invention.
- the proton conductive membrane of the present invention has an organic-inorganic composite structure having a cross-linked structure by metal-oxygen bond and a continuous pore structure in which pores formed inside by the bridge structure are continuously connected.
- a support structure composed of a body (h) is filled with a proton conductive structure (3) including an acid-containing structure containing an acid group.
- the organic-inorganic composite structure ( ⁇ ) holds the proton conductive structure ( ⁇ ) (hereinafter sometimes referred to as an electrolyte material or an electrolyte) and plays a role in improving the physical properties of the membrane.
- electrolyte material hereinafter sometimes referred to as an electrolyte material or an electrolyte
- the requirements for supporting the electrolyte are as follows.
- the significant physical properties of the support are determined by the physical properties of the electrolyte to be filled. That is, when the electrolyte is, for example, a non-crosslinked polymer electrolyte (for example, a perfluorinated alkylsulfonic acid polymer or a sulfonated aromatic polymer), the role of the support is to prevent swelling deformation, and to provide a membrane after swelling. The main role is to maintain the strength of steel, and strength is required.
- a non-crosslinked polymer electrolyte for example, a perfluorinated alkylsulfonic acid polymer or a sulfonated aromatic polymer
- the electrolyte is a crosslinked product (for example, a phosphoric acid composite silica crosslinked product, a sulfonate composite organic-inorganic composite crosslinked product, etc.) and has fragility
- the support is The main role is to prevent breakage due to stress dispersion, and flexibility is required.
- the organic-inorganic composite structure ( ⁇ ) used in the proton conductive membrane of the present invention has both a flexible organic site and a strong cross-linked site, the non-cross-linked polymer electrolyte
- the organic-inorganic composite structure (o can be effectively used as a support for a crosslinked electrolyte in a high-temperature operating fuel cell or a direct fuel supply type fuel cell.
- the support is also required to be stable under such high temperature, high humidity, high concentration acid, and oxidation conditions.
- the organic-inorganic composite structure of the present invention (c is stabilized by a so-called inorganic cross-link such as a metal-oxygen bond, for example, a silicon-oxygen bond, an aluminum-oxygen bond, a titanium-oxygen bond, a zirconium-oxygen bond, etc. Because it is a material, it does not dissolve or decompose even at high temperatures, has little swelling even at high humidity, minimizes hydrolysis even at high concentrations of acid, and is stable under oxidizing conditions. Can be suitably used.
- each of the support and the electrolyte needs to have a function of shutting off fuel, but the organic-inorganic composite structure of the present invention ( ⁇ is Due to its dense structure, the permeability of gaseous fuels such as hydrogen gas can be kept extremely low, and even in the case of direct fuel type fuel cells using liquid fuels such as methanol, dimethyl ether and hydrocarbons, Since the organic-inorganic composite structure () of the present invention has a dense structure due to inorganic cross-linking, there is very little transformation or swelling of the support due to fuel or permeation of fuel.
- the support for supporting the electrolyte material has an affinity for the electrolyte material and has sufficient adhesion to the electrolyte material. That is, when the support and the electrolyte material do not have adhesion, the support and the electrolyte material may be separated or broken at the interface due to various stresses in the operation of the fuel cell. this If such separation or rupture occurs, the separation or rupture may cut the ion conduction path or cause fuel to leak through the separation surface.
- the organic-inorganic composite structure of the present invention ( ⁇ has both an organic portion and an inorganic portion and has a good affinity for both organic polymer electrolytes and inorganic electrolytes.
- the fuel cell has a feature that it maintains a stable shape even under operating conditions and that it can disperse stress such as deformation of the electrolyte, so that peeling and breaking are extremely unlikely to occur.
- bonding between the support and the electrolyte is performed to ensure adhesion, but in such a method, the selection range of the support and the electrolyte is limited and Since activation (such as plasma treatment in the above-mentioned publication) is required, the process becomes complicated and cost increases.
- the organic-inorganic composite structure (a) of the present invention does not require such treatments as plasma treatment, and can be formed by simple steps, and does not cause a rise in cost.
- the organic-inorganic composite structure ( ⁇ ) used for the proton conductive membrane of the present invention has a crosslinked structure formed by a metal-oxygen bond and an organic structural portion, and the pores formed therein by the crosslinked structure are continuously formed. It has a connected continuous pore structure.
- the ratio between the organic-inorganic hybrid structure and the cross-linked structure due to the metal-oxygen bond in the organic-inorganic composite structure (c) depends on the proton conductive structure (J3) to be filled, the operating conditions of the fuel cell (temperature, humidity, Depending on the composition and structure of the metal-oxygen bond or the composition and structure of the organic structure, the physical properties obtained differ depending on the composition and structure of the organic structure. In general, when the number of cross-linked structures increases, the heat resistance and the film strength improve, while when the number of organic structures increases, the properties become more flexible.
- the ratio of the inorganic crosslinked structure portion to the organic structure portion can be arbitrarily determined according to the type of the organic-inorganic composite structure (the metal atom and the carbon atom in the organic-inorganic composite structure (c).
- the composition has more carbon atoms than this, the effect of crosslinking is reduced, heat resistance, fuel stability, etc. are reduced, and the structure ( ⁇ may be modified or deformed at high temperature operation). In addition, there is a possibility that swelling due to fuel may occur and this may contribute to fuel leakage.
- the metal atom in the organic-inorganic composite structure ( ⁇ ) can be used without any particular limitation as long as it forms a metal-oxygen bond. Among them, it is relatively easy to obtain and handling is easy. Simple silicon, aluminum, titanium, and zirconium can be preferably used. Among them, silicon is particularly preferably used because it is particularly inexpensive, has moderate reactivity, and a wide variety of structures can be obtained.
- a silicon-oxygen bond is particularly preferably used.
- the metal other than the above-described silicon, or , Phosphorus, boron and the like may be used in combination.
- the organic-inorganic composite structure ( ⁇ ) of the present invention may impart proton conductivity by compounding an acid group or the like, but may have proton conductivity in consideration of heat resistance, dimensional stability, and gas barrier properties. It is preferable to use without giving. If the structure (c) does not have proton conductivity, the structure () becomes a non-ion conductive phase. Therefore, when the volume fraction of the structure ( ⁇ ) in the film increases, the proton conduction performance of the entire film increases. Therefore, the volume ratio (porosity; space filled with the proton conductive structure ( ⁇ )) of the continuous pores in the structure (h) should be higher than a specific ratio.
- the required pore volume ratio depends on the performance of the electrolyte to be filled, it cannot be specified unconditionally, but specifically, it is preferably in the range of 20 to 95% by volume. Less than 0% by volume Then, the non-ion conductive portion in the film becomes too large, and the proton conductive film of the present invention cannot obtain high ionic conductivity. Meanwhile, 9 5 capacity. If the ratio exceeds / 0 , the composite effect of the structure (a) is reduced, and the ability to strengthen the electrolyte or disperse the stress cannot be exhibited, and the physical properties of the proton conductive membrane are likely to be reduced.
- the pore size of the continuous pores of the organic-inorganic composite structure ( ⁇ ) of the present invention is preferably in the range of 0.01 to 10 / ⁇ ).
- ⁇ is preferred, and more preferably 0.05 to lxm.
- the organic-inorganic composite structure (0!) of the present invention includes an inorganic crosslinked structure formed by a metal-oxygen bond and an organic structure.
- the inorganic crosslinked structure and the organic structure may be bonded to each other or may not be bonded to each other. However, considering the stability of the structure ( ⁇ ) and the uniformity of performance, the organic structure and the organic structure may be combined. It is preferable that the crosslinked structure is bound by a covalent bond.
- the bond between the organic structure and the inorganic structure may be bonded via an oxygen atom or the like, as in the case of metal-oxygen-carbon (for example, Si-o-c). there is a possibility. Therefore, more preferably, the metal and carbon are directly covalently bonded.
- Examples of such a bond include a Si—C bond and a Ti—C bond.
- a bond having a Si—C bond from which a wide variety of compounds are available can be particularly preferably used.
- the compound having a Si—C bond is not particularly limited, and a mono-, di-, or tri-alkylsilane compound can be used.
- the organic-inorganic composite structure satisfying the porosity and the pore size is preferable. It has a high ability to form a body ( ⁇ ) and can be preferably used.
- the reason why the compound of the formula (1) forms such a particularly preferable structure is considered to be due to the balance between the compatibility with the solvent used in the production and the reactivity.
- M is a silicon atom
- X is a single O-bond or OH group involved in crosslinking
- R 1 is carbon atom-containing molecular ⁇ 1 to 50 carbon atoms
- R 2 is methyl, Echiru, propyl Le or phenyl group
- nl, 11 2 is 0, 1 or 2
- eta 1, eta 2 at least
- each structure is 1, 2, ⁇ , i, ⁇ , , P, and the expression
- ⁇ represents the number of types of compounds corresponding to the chemical formula (1) contained in the organic-inorganic hybrid structure ( ⁇ , and represents an integer of 1 or more, and ⁇ represents an integer of 1 to ⁇ .
- ⁇ 1 i and 112 1 represent n 1 and n 2 in the above chemical formula (1) in the organic-inorganic composite ( ⁇ ) i, and are 0, 1 or 2 and n 1 1 and n 2 At least one of the 1 1 or 2, and mi represents a mole fraction).
- n 1 i, n 2 1 the organic-inorganic composite in (a) i, represents n 1, n 2 that put the above formula (1), 0, 1 or 2, and n 1 1, at least one of n 2 1 is 1 or 2, and mi represents a mole fraction).
- the formula (II) is 3.0, it is easy to form a continuous pore structure.
- nl and n2 are 1 or 2.
- R 1 is a molecular chain having a carbon atom and has a function of controlling the flexibility and crosslink density of the obtained film.
- flexibility may become impossible expression, or an unstable compound soluble
- R 1 is preferably a carbon atom-containing molecular chain group having 1 to 50 carbon atoms. More preferably, it has 4 to 12 carbon atoms.
- R 1 is preferably a hydrocarbon chain. This is because when R 1 has a heteroatom, the compound may be cleaved by an acid or heat.
- hydrocarbon chains are less susceptible to acid attack. Examples of such hydrocarbons include an alkylene chain and an aromatic chain. Among these hydrocarbons, particularly preferred is a linear molecular chain composed of a polymethylene chain having no branched chain. The polymethylene chain having no branched chain has the following formula:
- R 1 is a compound group that is a linear polymethylene group as shown in chemical formula (5), it is stable against attack by acids and radicals, and is a proton conductive membrane for heat-resistant fuel cells. Can be preferably used.
- linear polymethylene chain has a bendable structure, it is possible to impart appropriate flexibility to the obtained film, and it is possible to adjust the denseness and the like. These adjustments are mainly affected by the molecular length of the polymethylene chain.
- m is in the range of 4 to 12, and for example, an otatamethylene group having m of 8 can be preferably used because a commercially available raw material can be used. They can satisfy all of heat resistance, flexibility, and fuel gas barrier properties.
- R 1 has a branched chain
- the methine hydrogen in that portion is subjected to extraction by active radicals and the like generated during the operation of the fuel cell, and as a result, is cut as it is or an unsaturated bond Which can be further broken by oxidation There is a potential.
- R 1 may contain an aromatic compound group, but when the aromatic and silicon atoms are directly bonded, the aromatic ring is cationized and the bond with the silicon atom is broken.
- the benzyl position becomes the active site, and decomposition or reaction may occur during long-term use.
- R 1 may have a heteroatom, an aromatic ring, or a branched structure, but may be added as long as the physical properties of c are not impaired, but R 1 is mainly composed of straight methylene It is more preferable that all are linear methylene.
- the organic-inorganic composite structure ( ⁇ ;) is not limited to a crosslinked crosslinked structure, but has various metal-oxygen bonds or has a metal-oxygen bond.
- an organic-inorganic composite structure (a bridge-type crosslinked structure in ⁇ is preferably 5 0 wt% or more, more preferably 80 wt% or more It is preferable that these weight% can be adjusted by mixing the raw materials at the time of production.
- Materials other than the cross-linking type crosslinking agent include, for example, metal-oxygen cross-linked structures such as titanium, zirconium, and aluminum, and silicon-metal cross-linked structures and their alkyl-substituted mono- and di-alkyl compounds. Be You.
- the proton conductive membrane of the present invention has an organic-inorganic composite structure having a cross-linked structure by metal-oxygen bond and a continuous pore structure in which pores formed inside by the bridge structure are continuously connected.
- a support structure consisting of a body (h) is filled with a proton conductive structure () containing an acid-containing structure containing an acid group.
- the proton conductive structure (i3) is a material that plays a major role in proton conduction from the anode to the force sword.
- Many proton conductive materials are already known.For example, sulfonic acid was introduced into the side chain of fluororesin. Ont Co., Ltd.), Acip 1 ex (Asahi Kasei Co., Ltd.), F remion (Asahi Glass Co., Ltd.), as well as those in which sulfonic acid is introduced into an aromatic polymer side chain are known. .
- these known proton conductive materials may be introduced into the organic-inorganic composite structure ( ⁇ ). It offers many advantages such as stress dispersion function, durability against high temperature, high humidity, high concentration acid and oxidation, fuel barrier property, and affinity with electrolyte.
- a more preferred proton conductive structure (/ 3) has a crosslinked structure.
- This crosslinked structure is an important component for the proton conductive film of the present invention, and plays a role in, for example, mechanical strength, heat resistance, durability, and dimensional stability of the film.
- Neither the conventional fluororesin-based membrane nor the proton conductive membrane made of a polymer material having an aromatic molecular structure in the main chain has a crosslinked structure. Therefore, at high temperatures, the structure of the membrane changes significantly due to the cleaving phenomenon and the like, and as a result, the operation of the fuel cell at high temperatures becomes unstable.
- a Nafion (registered trademark) film manufactured by DuPont
- a fluororesin-based film is a strong and flexible film when dry, but swells greatly when wet.
- MEA membrane-electrode assembly
- the membrane always expands and contracts in response to changes in the temperature and humidity inside the fuel cell due to changes in operating conditions, which may cause membrane breakage and MEA rupture.
- the membrane becomes weak at the time of swelling, not only the dimensional change described above but also the risk of the membrane being broken when a pressure difference occurs in the fuel cell may occur.
- the Nafion membrane is kept in a wet state at a high temperature of, for example, about 150 ° C. for a long time, it becomes jelly-like and the membrane itself breaks down, so that it cannot be used as a fuel cell membrane. Further, even at a temperature of about 120 ° C., a transformation to a swollen state occurs due to the creep phenomenon. Once denatured, if the membrane dries due to changes in the operating conditions of the fuel cell, it will become a hard and brittle membrane, breaking or cracking the membrane, and even breaking the membrane-electrode assembly Can happen. This also occurs in a film having an aromatic molecular structure in the main chain.
- a crosslinked structure that is, if the crosslinked structure is introduced at a sufficient density, a large dimensional change is not observed and no change in strength occurs in a wet state or a dry state.
- an organic cross-linking material such as an epoxy resin, a cross-linkable acryl resin, a melamine resin, or an unsaturated polyester resin can be used. It is difficult to obtain long-term stability when exposed to high temperature and high humidity under the conditions of (proton).
- a crosslinked structure consisting of metal-oxygen bonds, such as silicon-oxygen bonds, aluminum-oxygen bonds, titanium-oxygen bonds, zirconium-oxygen bonds, etc. It is relatively stable even in an environment and can be suitably used as a crosslinked structure inside a fuel cell membrane.
- a silicon-oxygen bond can be easily obtained, and is inexpensive, so that it can be particularly preferably used.
- a silicon-oxygen bond is mainly used, but the metal-oxygen bond other than the aforementioned silicon or the phosphorus-oxygen bond may be used without sacrificing cost and ease of the manufacturing method.
- a bond or a boron-oxygen bond may be used in combination.
- the ratio of silicon-oxygen bond in the crosslinked structure is not particularly limited.
- the atomic ratio of “silicon” to “elements other than silicon that binds to oxygen (metals other than silicon, phosphorus, boron, etc.)” is usually 5% when 100% of all metal atoms are 1%.
- the material becomes hard and brittle, resulting in a material, which may be difficult to handle as a single film.
- the pores of the organic-inorganic composite structure ( ⁇ ) are filled with the proton conductive structure (). Then, stress is dispersed by the flexibility of the organic-inorganic composite structure (a), and a proton conductive film that is easy to handle can be obtained.
- the proton conductive membrane In order for the proton conductive membrane to exhibit high conductivity, and exhibit heat resistance, durability, dimensional stability, and fuel barrier properties, it is preferable that the following requirements are satisfied.
- the proton conductive structure (/ 3) is not particularly limited as long as it has proton conductivity.
- the proton conductive structure preferably has an acid group and has a Si—O bond. More preferably, it contains an acid group-containing structure (A) having a structure bonded to the crosslinked structure of the membrane, for example, having a structure represented by the following chemical formula (3). ,,, ⁇
- M is a silicon element
- X is a single O— bond or an O H group involved in crosslinking
- R 3 represents a molecular chain group having at least one acid group
- R 4 represents a methyl, ethyl, propyl or fuel group
- m represents 0, 1 or 2.
- R 3 has at least one or more acid groups, and is a group bonded to a crosslinking group by a covalent bond.
- the acid group various acids such as sulfonic acid, phosphonic acid, carboxylic acid, sulfuric acid, phosphoric acid, and boric acid can be used.
- pKa is low, and the proton concentration in the membrane can be sufficiently ensured and the heat can be maintained.
- Sulfonic acid which is also stable is preferably used.
- the proton conductive membrane of the present invention fills the organic-inorganic composite structure (h) with a proton conductive structure ( ⁇ ) containing an acid-containing structure having an acid group. (/ 3) are structures that have invaded each other.
- Proton conductive membranes for fuel cells need to conduct protons efficiently. Basically, the proton concentration in the membrane, the amount of the transfer medium (eg, water) and the movement Therefore, it is desirable that protons be present at a high concentration in the membrane. For this purpose, it is necessary to arrange as many acid groups as possible in the membrane.
- Such acid groups are extracted from the membrane by water supplied to the fuel cell or water generated during the operation of the fuel cell, and when the acid groups are dissipated, the proton concentration in the membrane decreases, resulting in proton conductivity. Decreases. For this reason, it is preferable to fix the acid by a covalent bond so that the acid does not remain in the membrane due to ionic interaction or the like but stays in the membrane stably for a long period of time.
- the acid group-containing structure ( ⁇ ⁇ ⁇ ⁇ ) included in the proton conductive structure ( ⁇ ) has a structure having sulfonic acid and being bonded to a metal-oxygen bridge. More preferably, R 3 in the chemical formula (3) preferably has a structure represented by the following chemical formula (12).
- n is an integer of 1 to 20.
- the structure that bonds the sulfonic acid to the crosslinked structure is not particularly limited, but for the purpose of the present invention, it is necessary to have excellent heat resistance, acid resistance, oxidation resistance, and the like.
- a methylene chain can be preferably used.
- the methylene chain is not branched, and that a sulfonic acid group is present at the end of the polymethylene chain.
- the methine structure at the branch is susceptible to oxidation and radical reaction, and as a result, sulfonic acid is dissipated from the membrane, which is not preferable.
- the sulfonic acid binding part has a methine structure, so that the sulfonic acid is desorbed and dissipated by oxidation as in the case of branching. This is because
- the acid group-containing structure (A) that binds the sulfonic acid to the crosslinked structure does not contain an aromatic ring.
- Such a direct sulfonation of an aromatic compound is easy to synthesize, but has the disadvantage that it is also easily desorbed. Easy desulfonation when operating fuel cell This is because a reaction occurs, and the conductivity decreases.
- the acid group-bonded structure of the acid group-containing structure (A) preferably used in the present invention has the structure represented by the chemical formulas (3) and (12).
- n is 1 to 20, and more preferably, n is 1 to 12.
- n is 0, that is, a compound in which a sulfone group is directly bonded to a silicon atom because the compound is easily hydrolyzed. If n is more than 20, it is not preferable because the crosslink density of the membrane is reduced.
- 3-trihydroxysilylpropylsulfonic acid which is a raw material of the structure in which n is 3, is commercially available from Gelest, and a synthesis method using aryl bromide as a raw material. Has been established, and can be used particularly preferably because it is easily available.
- the functional group in which a silicon atom in the acid group-containing structure (A) participates in crosslinking 2 or 3 is preferably used. It can be used even when the number of functional groups involved in cross-linking is 1, but in this case, the structure seals the cross-linking, so a large amount of structure (A) is introduced to secure a sufficient amount of acid As a result, insufficient cross-linking occurs and the film does not become a film or a film with low durability. Even when the number of functional groups involved in crosslinking is 1, it is possible to introduce them within a range that does not greatly affect the physical properties of the film.
- crosslinking density can be achieved, and therefore, it can be particularly preferably used. Since those having two functional groups in which the silicon atom participates in cross-linking have a linear structure, other cross-linkable structures and structures (A) in which the functional group involved in the cross-linking group is 3 are used in combination. Is preferred.
- the silicon atom of the acid group-containing structure (A) has two functional groups involved in cross-linking, in addition to the bond with the cross-linking group and the bond having a sulfonic acid group via a methylene group, Any substituent selected from stable substituents under high-temperature, high-humidity, and strong acid conditions such as an alkyl group may be provided, and among them, a methyl group is easily available as a raw material and can be preferably used.
- an OH group which has not completed the bonding reaction with the crosslinked structure may remain on the silicon atom of the acid group-containing structure (A).
- the proton conductive structure (/ 3) may contain a metal-oxygen bond structure (B) in addition to the acid group-containing structure (A).
- a metal monooxygen bond structure (B) separately from the acid group-containing structure, the crosslink density and the like can be adjusted, and the physical properties of the proton conductive structure (jg) as a whole (eg, flexibility) ) Can be changed as needed.
- the metal-oxygen bond structure (B) is not particularly limited as long as it forms a metal-oxygen bond.
- a structure represented by the following chemical formula (2) is used. Can be done.
- R 2 is methyl, Echiru, propyl or Hue - indicates any group Le group, ni, 11 2 is 0, 1 or 2.
- the compound represented by the chemical formula (2) is the same as the organic-inorganic composite structure (the cross-linked cross-linked structure (1) used in ⁇ ).
- R 1 in the compound of formula (2) is the same as the organic-inorganic hybrid structure ( ⁇ ).
- a methylene chain is preferable under high temperature, strong acid and oxidizing conditions, and the length of the methylene chain is also preferably 1 to 50, more preferably 4 to 12.
- cross-linked cross-linked structure (2) is used for the proton-conductive structure ()
- the number of terminal cross-links is no limitation on the number of terminal cross-links as in the case of the organic-inorganic composite structure (H), and the required physical properties are different. It can be freely selected according to the situation.
- metal-oxygen bond structure ( ⁇ ) a compound represented by the following chemical formula (6) may be used.
- M is a metal atom
- X is a 0-bond or an OH group involved in crosslinking
- R 2 is any group of methyl, ethyl, propyl or phenyl group
- m is 0, 1 or 2
- metal atom M aluminum, titanium, zirconium, and silicon can be preferably used as the metal atom M.
- silicon that is inexpensive, easy to adjust the reaction, and can use many derivatives
- R 2 in the formula (6) may be any as long as it contains an arbitrary organic group, but in consideration of high-temperature stability and the density of a crosslinking group, it is preferable to use a substituent such as methyl, ethyl, propyl, and phenol. Can be done.
- the metal-oxygen bond structure (B) may be a mixture of the above-mentioned bridge-type crosslinked structure (2) or a structure represented by the chemical formula (6). It may include a bridged bridge structure (2) or a structure represented by a plurality of chemical formulas (6).
- the ratio of the acid group-containing structure ( ⁇ ) to the metal-oxygen bond structure ( ⁇ ) in the proton conductive structure ( ⁇ ) can be arbitrarily determined according to the intended use. A larger number of bodies ( ⁇ ) improves proton conductivity, while a larger number of metal-oxygen bonded structures ( ⁇ ) can increase structural stability. Therefore, the ratio of ( ⁇ ) to ( ⁇ ) is determined as appropriate according to the conditions of use, and cannot be unambiguously determined.
- the weight ratio of ( ⁇ ) in ( ⁇ ) is 0 to 95%. Preferably, there is.
- ( ⁇ ) is not included, the proton conduction performance is maximized, but durability and physical properties are reduced, so that it is suitable for mild fuel cell operation conditions. Since the durability and physical properties can be adjusted, it is possible to obtain a proton conductive membrane that can withstand more severe fuel cell operating conditions.
- the weight ratio of ( ⁇ ) exceeds 95%, the proton conductivity becomes too low, which is not preferable.
- the acid group-containing structure ( ⁇ ) and the metal-oxygen bond structure ( ⁇ ) in the proton conductive structure (0) may be uniformly dispersed, or may have a localized phase structure. It may be. In the case of uniform dispersion, the stability is good, and in the case of localization, the conduction performance is improved.
- an organic-inorganic composite structure (ce) is prepared in advance, and the raw material composition of the proton conductive structure (3) is filled in advance. Can be preferably used.
- the step of preparing a mixture containing an organic-inorganic composite crosslinkable compound (C) having a crosslinkable silyl group at its end and a carbon atom covalently bonded thereto, and a step of preparing the mixture It is manufactured by a method including a step of forming a film and a step of hydrolyzing and / or condensing a crosslinkable silyl group contained in the formed mixture.
- the organic-inorganic composite crosslinkable compound (C) is not particularly limited as long as it has a crosslinkable silyl group and a carbon atom covalently bonded thereto.
- a cross-linking agent represented by the following formula (4), which is a raw material of the cross-linked structure, can be used.
- R 5 is Cl, OCH 3 , OC 2 H 5 , OC 3 H 7 ,
- R 1 is a carbon atom-containing molecular chain group having 1 to 50 carbon atoms
- R 2 is a methyl, ethyl, propyl or phenyl group
- n 1 and n 2 are 0, 1 or 2
- at least one of n 1 and n 2 represents 1 or 2.
- the compound represented by the chemical formula (4) is an organic-inorganic composite structure (the chemical formula (1) described in c). Is a raw material for the crosslinked structure of
- the number of hydrolyzable groups R5 that are the origin of X is preferably such that a in Formula (II) is between 2.9 and 3.5, and more preferably a value close to 3.0.
- P is an organic-inorganic composite crosslinkable compound type an integer of 1 or more to a number of (C), also i represents an integer of 1 to P, n 1 1, n 2 1 is In the organic-inorganic hybrid bridging compound (C) i, nl and n2 in the above chemical formula (4) are represented by 0,
- nl that at least one of n 2 is 1 or 2
- a crosslinking type crosslinking agent corresponding to the chemical formula (4) having a plurality of different numbers of hydrolyzable groups is mixed.
- R 1 is rather preferably be a carbon-containing molecular chain group of 1-50 carbon atoms, be more preferable still is a number from 4 to 1 2 carbon atoms, or, R 1 is charcoal
- a hydrocarbon chain is preferable, and among hydrocarbons, a linear molecular chain composed of a polymethylene chain having no branched chain represented by the chemical formula (5) is preferably used. The same is true.
- n indicates an integer of 1 to 20
- R 1 is a straight
- R J is a straight
- the main component be linear methylene, and it is more preferable that all methylenes be linear methylene.
- cross-linking cross-linking agent represented by the above formula (4) a commercially available cross-linking agent can be used.
- the cross-linking cross-linking agent can also be obtained by a hydrosilylation reaction of a hydrolyzable silyl group of a compound having a corresponding unsaturated bond. Can also be used in combination.
- R 1 examples include ethylene, hexamethylene, otatamethylene, and nonamethylene, which are commercially available from Gelest (Gelest).
- Examples of compounds that can be synthesized include hydrosilylation reaction of 1,3-butadiene, 1,9-decadiene, 1,13-tetradecadiene, and the like.
- R 1 is a raw material corresponding to tetramethylene, decamethylene, or tetradecamethylene
- the polymethylene chain having up to 20 carbon atoms can be easily synthesized, and the chemical formula (4) It is possible to obtain a crosslinking agent corresponding to the above.
- Examples of specific compounds include bis (diethoxymethylsilyl) ethane, bis (diethoxymethylsilyl) hexane, bis (diethoxymethylsilyl) otatan, bis (diethoxymethylsilyl) nonane, Bis (dimethylethoxysilyl) ethane, bis (dimethylethoxysilinole) hexane, bis (dimethylethoxysilyl) octane and the like can be used, and these can be used alone or in combination.
- the organic-inorganic composite structure ( ⁇ is not limited to a cross-linked cross-linked structure, but has various metal-oxygen bonds, or has a metal-oxygen bond.
- an organic group containing an organic group such as titanium alkoxides such as titanium tetrabutoxide and titanium tetrapropoxide, zirconium alkoxides such as zirconium tetraisopropoxide, and aluminum triisopropane.
- Hydrolyzable metal compounds such as aluminum alkoxides such as propoxide, or complexes thereof may be mixed.
- Triethoxysilane etc. Monoalkyl-substituted alkoxysilanes, Jimechirujime Tokishishiran, dialkyl-substituted alkoxysilanes such as Jechiru trimethylamine Tokishishiran, or may be like is added oligomers thereof.
- the crosslinking type crosslinking agent (4) is preferably incorporated in the organic-inorganic composite structure ( ⁇ ) in an amount of preferably at least 50 wt%, more preferably at least 80 wt%. As described above, it is preferable that the content is not less than%. This weight% can be adjusted by blending these raw materials.
- the method includes a step of preparing a mixture containing the following. In the mixing step, any method can be used.
- the optional method includes a method using a normal stirring blade or a stirring bar, a method using a dissolver, a vibration method, an ultrasonic method, and the like, but is not limited thereto, and a method of uniformly mixing. Should be fine.
- alcohols such as methanol, ethanol, isopropanol and ⁇ -butanol
- ethers such as tetrahydrofuran and dioxane can be used, but are not particularly limited as long as the raw material mixture to be used can be uniformly dissolved.
- the amount of the solvent is 0.5 to 10 ml / g, preferably 1 to 5 ml / g, based on the solid content (g) of the organic-inorganic composite crosslinkable compound (C). pore Desirable for forming structures.
- the amount is less than the above range, it is difficult to form a continuous pore structure in the obtained structure (c), and even if it is formed, the porosity becomes small, and conversely, the structure obtained becomes large. It is difficult for the body () to form a continuous pore structure, and even if it is formed, the strength as a support cannot be satisfied.
- the mixed solution of the organic-inorganic composite crosslinkable compound (C) obtained in the above step is formed into a film by a known method such as a casting method or a coating method.
- the method for forming a film is not particularly limited as long as a uniform film can be obtained, and any method can be used.
- the thickness of the formed film is appropriately determined from the proton conductivity and fuel permeability of the resulting proton conductive membrane, and the mechanical strength of the membrane, and cannot be specified unconditionally.
- the crosslinkable silyl group contained in the formed organic-inorganic composite crosslinkable compound (C) is specifically converted into a compound (C) by a so-called sol-gel (so1-ge1) reaction.
- a hydrolyzable silyl group is hydrolyzed and condensed or, if the crosslinkable silyl group is a silanol group ⁇ silanolate group, only condensed to form a crosslinked structure comprising a silicon-oxygen bond.
- hydrolysis and condensation can be carried out by the same reaction even if alkoxides such as titanium, zirconium, and aluminum are added.
- the continuous pore structure having the pore diameter and the porosity formed in the organic-inorganic composite structure ( ⁇ ) has a phase with the solvent due to an increase in the molecular weight of the support due to the condensation reaction. It is formed using separation. Therefore, the formation of the three-dimensional network structure greatly depends on the hydrolysis rate and the condensation reaction rate, and the temperature and catalyst concentration are appropriately adjusted. It is necessary to save.
- the support is cured at a boiling point of the solvent of 300 ° C., preferably 100 ° C. to 200 ° C., whereby a support having a three-dimensional network structure is obtained.
- a membrane can be obtained.
- the obtained proton conductive membrane of the present invention is used at a high temperature of 100 ° C. or higher, it is preferable to crosslink by heating at a temperature condition higher than the use temperature. Such heating may be carried out even if the crosslinking step is carried out at 100 to 300 ° C., or the crosslinking reaction is carried out, for example, at 5 to 40 ° C.
- the crosslinked structure can be immobilized. If the temperature is too low, the crosslinking reaction will be slow, and if the temperature is too high, the organic portion may be degraded.
- heating method known methods such as heating in an oven, heating under pressure using an autoclave, far-infrared heating, electromagnetic induction heating, and microwave heating may be used alone or in combination.
- water may be added to the mixed solution in advance, or the crosslinking reaction may be carried out while heating under steam.
- a catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, etc. was previously added to the reaction system. It is desirable to add a Sted acid.
- a base catalyst such as ammonia or sodium hydroxide may be used.
- the formation of a crosslinked structure support ( ⁇ ) having a three-dimensional network structure is a blended process. Acid catalysts are preferably used.
- the concentration is preferably 5 N or more and less than 10 N. If the concentration is lower than the force range, the reaction becomes slow and it is difficult to obtain a desired network structure. On the other hand, if the concentration is higher than the above range, the reaction is too fast to form the desired network structure. It is difficult and unfavorable. Further, the addition amount of the Prensted acid catalyst preferably satisfies the relationship represented by the following formula. z (ac-Nc Mc)
- the amount of the Prensted acid catalyst to be added is less than the amount that satisfies the above formula (III), the hydrolysis rate is too small and the crosslink density becomes small. Does not form a network structure.
- the numerical values 0.5 and 1.5 represent the number of equivalents of water in the aqueous solution of the Prensted acid catalyst with respect to the crosslinkable silyl group, respectively. Means that the same amount of water as in the case of hydrolyzing the crosslinking group is added.
- the reaction is promoted by adding a Bronsted acid
- the temperature is higher than the freezing point of the solvent and lower than the boiling point of the solvent, preferably 0 to It is preferably carried out at a temperature around 40 ° C.
- organic-inorganic composite structure ( ⁇ ) membrane as a support can be washed with metal ion-free water, such as distilled water or ion-exchanged water, if necessary. .
- the obtained organic-inorganic composite structure (c film may be further irradiated with an ultraviolet ray or an electron beam to complete the crosslinking.
- the proton conductive membrane of the present invention is manufactured by filling the fine pores of the organic-inorganic composite structure (c) with the proton conductive structure (] 3).
- an existing non-crosslinked electrolyte resin for example, a fluororesin in which sulfonic acid is introduced into a side chain
- a resin dissolved in a solvent or the like is used as an organic-inorganic composite structure. It can be easily produced by filling in (a) and removing the solvent by heating or decompression.
- the proton conductive membrane of the present invention is intended to be used as a proton conductive membrane for a high-temperature operating fuel cell and a direct fuel (such as methanol) type fuel cell. It is preferable to use a proton conductive structure () in which the swelling of the film by the solvent is small, and therefore, it is preferable to introduce a crosslinked structure. It is difficult to fill a proton conductive membrane with a crosslinked structure into the micropores of the organic-inorganic hybrid structure ( ⁇ ) in a crosslinked state. This is because the bridged state is a state in which the proton conductive structure (0) is stabilized, so it is insoluble in the solvent, infusible, and has no degree of freedom to fill the pores. That's why.
- the precursor of the proton conductive structure having a cross-linking reactivity is used. It is preferable that the raw material is filled in (c) and a crosslinking reaction is performed after the filling. That is, the method for producing a proton conductive membrane of the present invention preferably comprises the steps of: An organic-inorganic composite is prepared by filling a mixture containing at least a crosslinkable silyl group and an acid group-containing compound (D) containing an acid group, and hydrolyzing and / or condensing the crosslinkable silyl group contained in the filled mixture. Forming a crosslinked structure of the proton conductive structure (] 3) inside the structure ( ⁇ ).
- the acid group-containing compound (D) is not particularly limited as long as it contains a crosslinkable silyl group and also contains an acid group.
- a compound represented by the following formula (7) is exemplified. Is done.
- R 6 any group of OH, OCH 3 , OC 2 H 5 , OC 3 H 7 , R 3 : a molecular chain group having at least one acid group, R 4 : methyl, ethyl, A propyl or phenyl group; m represents 0, 1 or 2)
- the acid group of R those similar to those in the above formula (3) can be used, and a thermally stable sulfonic acid is preferably used.
- the compound corresponding to the chemical formula (7) may be an oligomer which has been condensed in advance.
- an oligomer When an oligomer is used, it may be a single oligomer of the compound of (7) or a mixed oligomer with another crosslinking agent.
- the acid group-containing compound (D) includes a compound having a structure represented by the following formula (8).
- R 3 is a molecular chain group having at least one acid group
- R 7 a group selected from the group consisting of H, CH 3 , C 2 H 5 S C 3 H 7 , C 4 H 9, and C 6 H 5 , and a branch partially forming one Si bond It may have a structure or an intramolecular cyclic structure.
- n and t they may be aggregates of compounds having the same or different values.
- the structure of the formula has the structure represented by the above formula (7) or (8), it is preferable that the structure of R 3 has the structure represented by the following formula (12). Raw material.
- n is an integer of 1 to 20.
- trihydroxysilylpropyl sulfone as the acid-containing compound (D) which is a raw material of the structure having n of 3
- the acid is commercially available from Gelest, and is easily available and can be particularly preferably used.
- Japanese Patent Application Laid-Open No. 54-138522 US Pat. , 152, 165
- a cross-linking agent represented by the following formula (4) is used. I can do it.
- M is a silicon
- R 1 R 2 and R 5 are used as the organic-inorganic composite crosslinkable compound (C) used in the production of the organic-inorganic composite structure ( ⁇ ).
- nl and n2 represent 0, 1 or 2.
- the compound represented by the chemical formula (4) is a raw material of the compound represented by the chemical formula (2).
- an organic-inorganic composite structure (the same crosslinking type cross-linking agent as used in ⁇ ) may be used.
- the compound represented by the above chemical formula (4) may be used alone or in combination of one or more.
- a cross-linking agent is separately used as a raw material of the proton conductive structure (] 3) in addition to the acid group-containing compound (D), for example, a cross-linking agent represented by the following chemical formula (16) is used. I can do it.
- M is a metal atom, R ⁇ OH OCH 3, OC 2 H 5, OC 3 H 7, OC 4 H 9, OC 6 H 5, any group of C and OCOCH 3 group
- R 2 is a methyl, ethyl, propyl or fuel group
- m represents 0, 1 or 2.
- the metal can be titanium, aluminum, zirconium, or the like.
- titanium alkoxides such as titanium tetrabutoxide and titanium tetrapropoxide
- zirconium tetraisopropoxide Hydrolyzable metal compounds such as zirconium alkoxides, aluminum alkoxides such as aluminum triisopropoxide, or complexes thereof can be used.
- M is preferably a silicon atom in the same manner as the above-mentioned structure, specifically, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, and methyltrimethylsilane.
- tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane
- methyltrimethylsilane examples include monoalkyl-substituted alkoxysilanes such as toxoxysilane, ethyltrimethoxysilane, and phenyltriethoxysilane; dialkyl / alkoxy-substituted alkoxysilanes such as dimethyldimethoxysilane and getyltrimethoxysilane; and oligomers thereof.
- the ratio of the acid group-containing structure ( ⁇ ) and the metal-oxygen bond structure ( ⁇ ) in the proton conductive structure ( ⁇ ) cannot be determined unconditionally.
- Weight Since the amount ratio is preferably 0 to 95 ° / o, the ratio of the acid group-containing compound (D) and the cross-linking agent, which are the raw materials, is affected by the molecular weight of the hydrolysis prayer. , 0 to 95%.
- the method for producing the proton conductive membrane of the present invention includes a step of preparing a mixture of the acid group-containing compound (D) and a crosslinking agent as an optional component. Can be done.
- the optional method includes a method using a normal stirring blade or a stirring rod, a method using a dissolver, a vibration method, an ultrasonic method, and the like, but is not limited thereto, and is a method of uniformly mixing. I just need.
- ethers such as tetrahydrofuran and dioxane can be used, but are not particularly limited as long as the raw material mixture to be used can be uniformly dissolved.
- the method of filling the obtained mixture into the micropores of the organic-inorganic composite structure ( ⁇ ) can be any method. If the mixture can be filled into the structure (c), any method can be used. The method may be used without particular limitation, and may be, for example, casting the mixture on a structure (o, or immersing the structure (c) in the mixture. The pressure may be reduced sometimes, and the temperature may be increased. The filling may be made to fit inside the structure (H), and the filling may be slightly applied (more than the thickness of c). Alternatively, a layer of the proton conductive structure () may be formed on the surface.
- the acid group-containing compound (D) and an optional cross-linking agent are filled in the organic-inorganic composite structure (o)
- the acid group-containing compound A step of crosslinking the compound (D) and an optional crosslinking agent is performed after the acid group-containing compound (D) and an optional crosslinking agent.
- a catalyst may be used.
- the catalyst include brenstead acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and acetic acid; inorganic base such as sodium hydroxide and ammonia; Known compounds such as organic bases such as triethylamine and getylamine can be used. In the method for producing a proton conductive membrane of the present invention, either of them can be used.
- the catalyst concentration can be arbitrarily determined in consideration of pot life, process suitability, and the like. Further, the catalyst may be previously contained in a mixture containing the acid group-containing compound (D), or may be exposed to a vapor containing the catalyst after filling.
- a fluoride such as fluorinated realm or ammonium fluoride may be used in combination.
- water used for hydrolysis may be used. Water may be contained in the mixture containing the acid group-containing compound (D) in advance, or may be exposed to steam after filling.
- heating may be performed.
- the temperature is equal to or higher than the boiling point of the solvent, and when no solvent is used, the temperature is equal to or higher than room temperature, and is equal to or lower than 300 ° C., preferably 100 to 100 ° C. It is desirable to heat at 250 ° C.
- the proton conductive membrane of the present invention is used at a high temperature of 100 ° C. or higher, it is preferable to crosslink by heating at a temperature condition higher than the use temperature.
- the heating time is not particularly limited, but is preferably about 5 minutes to 1 week.
- known methods such as open heating, autoclave pressure heating, far infrared heating, electromagnetic induction heating, and microwave heating may be used alone or in combination.
- the membrane obtained by the production method of the present invention may be washed with water or subjected to an acid treatment for protonation, if necessary.
- the proton conductive membrane of the present invention is manufactured by filling the fine pores of the organic-inorganic composite structure ( ⁇ ) with the proton conductive structure ().
- an acid group-containing compound (D) containing an acid and having a cross-linking group can be used as described above.
- An acid group precursor-containing compound (E) having a group that can be converted to an acid by hydrolysis, oxidation, or the like may be used.
- the group that can be converted into an acid group refers to an acid ester, an acid salt, a mercapto group, a sulfide group, and the like, which can be converted to a sulfonic acid by oxidation.
- the method for producing a proton conductive membrane according to the present invention is characterized in that the organic-inorganic composite structure ( ⁇ ) comprises an acid group precursor-containing compound containing at least a crosslinkable silyl group and an acid precursor group convertible to an acid group.
- the organic-inorganic composite structure ( ⁇ ) comprises an acid group precursor-containing compound containing at least a crosslinkable silyl group and an acid precursor group convertible to an acid group.
- the acid group precursor-containing compound (E) is not particularly limited as long as it contains a crosslinkable silyl group and contains an acid group precursor.
- it is represented by the following formula (7). Are exemplified.
- R 1 3 has at least one acid precursor
- R 4 represents a methyl, ethyl, propyl or phenyl group
- m represents 0, 1 or 2
- a phosphonate, a phosphonate, a carboxylic ester, a canoleponate, a sulfonate, a sulfonate, a sulfido group, a mercapto group, and the like can be used as the acid precursor group possessed by R ⁇ ⁇ ⁇ .
- a sulfonic acid ester, a sulfonic acid salt, a sulfide group, and a mercapto group that generate sulfonic acid are preferably used.
- the compound corresponding to the chemical formula (17) may be an oligomer that has been previously condensed.
- the oligomer is the same as the acid group-containing compound (D) in that it may be a single oligomer of the compound (17) or a mixed oligomer with another crosslinking agent.
- the acid group precursor-containing compound (E) includes a compound having a structure represented by the following formula (13).
- R 13 is a molecular chain group having at least one acid group precursor
- R 7 is a group selected from the group consisting of H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 and C 6 H 5 , and is partially —Si bond-branched It may have a structure or an intramolecular cyclic structure.
- R 8, R 9, R 10 , R 11 R °, OH, OCH 3, OC 2 H 5, OC 3 H 7, OC 4 H 9, OC 6 H 5, CH 3, C 2 H 5, C 3 It is a group selected from the group consisting of H 7 , C 4 H 9 and C 6 H 5 , and may have a branched structure partially having one OSi bond or an intramolecular cyclic structure.
- n Integer from 1 to 50
- n and t may be used.
- the polymer can have a structure similar to a random copolymer or a block copolymer.
- the proton conductive structure (] 3) can be more easily filled into the organic-inorganic composite structure (), and stable production can be achieved.
- the structure of the acid precursor-containing compound (E) is preferably such that R 3 in the above formula (17) is a structure represented by the following formula (15).
- n is an integer of 1 to 20.
- the group bonding the silicon atom and the acid precursor group is preferably a methylene chain, which is expected to have stability, and a carbon chain.
- the length is preferably 1 to 20 as in the case of the acid group-containing compound (D).
- the acid precursor group a mercapto group which can be easily converted to sulfonic acid by oxidation can be preferably used.
- Such an acid precursor group-containing compound (E) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, and 3-mercaptopropyltributoxysilane.
- 3-mercaptopropyl trimethoxysilane is inexpensive and easily available, and can be preferably used.
- an oligomer having the structure represented by the chemical formula (11) may be used as a raw material.
- 3-mercaptopropyl methoxide X-41-1805 product number
- a copolymer of silane and tetraethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
- a copolymer of 3-mercaptoprovir trimethoxysilane and methyltriethoxysilane X—41—1 810 product number
- SMS—992 product number
- a cross-linking agent is separately used as a raw material of the proton conductive structure ( ⁇ ) in addition to the acid precursor group-containing compound ( ⁇ ), for example, it is represented by the following formula (4) or (16) It is the same as the acid group-containing compound (D) in that a crosslinking agent can be used.
- R 6 is OH, OCH 3 , OC 2 H 5 , OC 3 H 7 ,
- the acid precursor group-containing compound (E) is used in the method for producing a proton conductive membrane of the present invention, a reaction for converting an acid precursor group to an acid group is required.
- an acid ester or an acid salt is used as an acid precursor group, an acid group is generated by ester hydrolysis or ion exchange by reacting with a Bronsted acid such as hydrochloric acid, sulfuric acid, nitric acid, or the like. Can be done.
- a sulfonic acid group can be obtained by oxidation.
- a general oxidizing agent can be used. Specifically, oxidizing agents such as nitric acid, hydrogen peroxide, oxygen, organic peracids (percarboxylic acids), bromine water, hypochlorite, hypobromite, potassium permanganate, and chromic acid Can be used.
- the membrane may be contacted with a strong acid such as hydrochloric acid or sulfuric acid.
- a strong acid such as hydrochloric acid or sulfuric acid.
- the protonation conditions such as acid concentration, immersion time, and immersion temperature are determined by the membrane. It is appropriately determined according to the sulfonic acid group content concentration in the solution, the porosity of the membrane, the affinity for the acid, and the like.
- the thus obtained proton conductive membrane of the present invention is flexible and It has a structure in which the proton conductive composition is highly filled, and the filled proton conductive composition is continuously connected in the thickness direction of the membrane, and has excellent proton conductivity.
- the resulting proton conductive membrane is an organic-inorganic composite membrane that has excellent heat resistance and durability, and exhibits excellent proton conductivity even at high temperatures, and can be suitably used as a proton conductive membrane for fuel cells. it can.
- a so-called membrane-electrode assembly in which the membrane and the catalyst-carrying electrode are joined is manufactured.
- This membrane-electrode assembly can be produced by appropriately using a known method such as a hot press method, a method of applying the proton conductive composition to the membrane and the electrode, or the like.
- the proton conductive membrane of the present invention can be used not only for an electrolyte membrane of a polymer electrolyte fuel cell but also for a chemical sensor diion exchange membrane and the like. Examples>
- the bending resistance of the proton conductive membrane was measured by the bending resistance test (cylindrical mandrel method) described in JIS K 5600-5-1. Using a type I mandrel (diameter 10 mm), evaluation was made according to the following evaluation criteria.
- a carbon paste (Conducting Grahite Paint; LADO RE SEARCH I NDUS) is provided on both surfaces of the proton conductive membrane of the present invention. (TR IES, INC) was applied and adhered to the platinum plate. The impedance of this platinum plate was measured in the frequency range of 0.1 Hz to 100 kHz using an electrochemical impedance measuring device (Model 1260, manufactured by Solartron) to evaluate the proton conductivity of the ion-conductive membrane. .
- the sample was supported in an electrically insulated sealed container, and the temperature of the cell was changed from room temperature to 160 ° C by a temperature controller in a steam atmosphere (95 to 100% RH).
- a temperature controller in a steam atmosphere (95 to 100% RH).
- the measured values at 60 ° C and 140 ° C are shown as representative values.
- the measurement was performed by pressurizing the inside of the measurement tank.
- the proton conductive membrane was heated in an autoclave at 140 ° C. for 5 hours under saturated steam.
- the evaluation after heating was conducted by visual inspection, dimensional measurement, and bending resistance test.
- the evaluation criteria were as follows.
- Dimethylethoxysilane was used instead of the above-mentioned ethoxymethylsilane.
- 1,8-bis (dimethylethoxysilyl) octane was obtained in exactly the same manner as above.
- a single-cell fuel cell was manufactured using the obtained membrane.
- the membrane obtained with a gas diffusion electrode (E-TEK, 2. Omg platinum-loaded product) was sandwiched, and this was introduced into a single cell (membrane area 5.25 cm ⁇ ) manufactured by E1 ectrochem, A cell fuel cell was made. With respect to the fuel cell thus obtained, hydrogen was introduced into the anode and oxygen was introduced into the power source, and an electronic load was connected to the output, and a voltage-current curve was measured.
- the obtained membrane was washed with running water at 80 ° C for 2 hours.
- the internal structure of this membrane was observed with an electron microscope, it was found that continuous pores with an average pore diameter of 50 O nm were densely filled with a resinous material as a proton conductor. It was confirmed that no peeling or cracking occurred at the interface of.
- Figure 1 shows the power generation evaluation
- Figure 2 shows the power generation evaluation
- a membrane was obtained in the same manner as in Example 1 except that the support prepared in the following method was used instead of the support of Example 1.
- the porosity and pore size of this support were measured with a porosimeter, and the internal structure was observed by SEM. As a result, it was confirmed that a continuous pore structure with a porosity of 60% by volume and an average pore size of 200 nm was formed. .
- the ratio of metal atoms to carbon atoms is about 1: 6.5.
- the value of a in equation (II) is about 3.1.
- Example 4 A membrane was obtained in the same manner as in Example 1 except that the support prepared in the following method was used instead of the support of Example 1.
- the obtained membrane was covered with a plastic case lid of 20 cm ⁇ 30 cm and cured at room temperature (20 ° C.) for 60 hours to obtain a white and rubbery support.
- the porosity and pore size of this support were measured with a porosimeter, and the internal structure was observed with an SEM. .
- the ratio of metal atoms: carbon atoms is about 1: 5.3.
- the value of a in equation ( ⁇ ) is about 3.0.
- the power generation evaluation was almost the same as in Example 2.
- the raw materials used were 0.6 g of 1,8-bis (diethoxymethylsilyl) octane, 0.5 g of 1,8-bis (dimethylethoxysilyl) octane and 0.05 g of tetraethoxysilane.
- the organic-inorganic composite structure (support Holding body) was formed. It was confirmed that this support had a continuous pore structure with a porosity of 60% by volume and an average pore diameter of 600 nm. In the resulting structure, the ratio of metal atoms: carbon atoms is about 1: 5. Furthermore, the value of a in equation ( ⁇ ) is 3.1.
- An organic-inorganic composite structure was produced in the same manner as in Example 1.
- Example 8 In the same manner as in Example 1, an organic-inorganic composite structure (support) was produced.
- Example 1 After mixing with a 5 ml methanol solution and stirring at room temperature for 5 minutes, the mixture was poured onto the prepared support and the film was cured and washed in the same manner as in Example 1.
- Example 1 1,8-bis (triethoxysilyl) octane 0.6 g and 1,8-bis (dimethinoleethoxysilyl octane 0.5 g instead of 1,8-bis (triethoxysilyl) octane 0. 65 ⁇ and 1, using 8-bis (dimethylamino ethoxy silyl) octane 0. 45 g, except for using hydrochloric acid 0. 27 g, attempted to cure in the same manner as in example 1. as a result , instead of the support of the white rubber, film that does not exhibit the white translucent rubber properties were obtained. the porosity of the membrane 20 volume 0/0, the average pore diameter was 30 nm.
- Example 2 In Example 1, 0.6 g of 1,8-bis (diethoxymethylsilyl) octane and 0.5 g of 1,8-bis (dimethylethoxysilyl) octane were replaced with 1,8_bis (triethoxysilyl) Curing was attempted in the same manner as in Example 1, except that 1.1 ⁇ of octane was used and 0.35 g of hydrochloric acid was used. As a result, a transparent and hard film was obtained instead of the white rubbery support. When the internal structure of the film was observed with an electron microscope, it was confirmed that the film was an aggregate of fine particles having a particle size of 10 to 50 nm. Further, the same proton conductive structure (conductive agent) as in Example 1 was added to this support, and curing and washing were performed in the same steps. The value of a in equation ( ⁇ ) is about 6.0. The evaluation results of the obtained film are shown below.
- a membrane was obtained in the same manner as in Example 1 except that the support prepared in the following method was used instead of the support of Example 1.
- the power generation evaluation shows that the gas barrier properties of the film of the present invention are ensured.
- an organic-inorganic material having a crosslinked structure by a metal-oxygen bond which is a constituent element of the present invention, and having a continuous pore structure in which pores formed inside by the crosslinked structure are continuously connected.
- the configuration in which a support made of a composite structure (h) is filled with a proton conductive structure () containing an acid-containing structure containing an acid group is used for a high-temperature durable proton conductive film.
- a free-standing membrane that exhibits stable proton conductivity from a low temperature to a high temperature and can be bent.
- the conventional fluorine-based membrane used as a typical electrolyte membrane has a high initial conductivity and relatively good conductivity after high-temperature durability, but the membrane undergoes large irreversible deformation.
- the deformed film was dried, it became a hard and brittle film, so it is clear that the conventional film cannot be used for PEFC that can operate at high temperatures.
- the proton conductive membrane of the present invention solves the above-mentioned problems in the conventional polymer electrolyte fuel cell, and is excellent in heat resistance, durability, dimensional stability, fuel barrier properties, flexibility, etc., and also at high temperatures. Since it exhibits proton conductivity, it can be usefully used in the field of fuel cells, especially in polymer electrolyte fuel cells.
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Abstract
Description
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Priority Applications (6)
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DE602004031330T DE602004031330D1 (de) | 2003-04-25 | 2004-04-23 | Protonenleitfähiger film, prozess zu seiner herstellung und brennstoffzelle mit dem protonenleitfähigen film |
CA002520827A CA2520827A1 (en) | 2003-04-25 | 2004-04-23 | Proton conducting membrane, method for producing the same and fuel cell using the same |
JP2005505878A JP4769577B2 (ja) | 2003-04-25 | 2004-04-23 | プロトン伝導性膜、その製造方法およびそのプロトン伝導性膜を用いた燃料電池 |
EP04729222A EP1619692B1 (en) | 2003-04-25 | 2004-04-23 | Proton-conductive film, process for producing the same, and fuel cell empolying the proton-conductive film |
US10/554,222 US20060219981A1 (en) | 2003-04-25 | 2004-04-23 | Proton conductive film, process for producing the same, and fuel cell employing the proton-conductive film |
KR1020057020209A KR101214319B1 (ko) | 2003-04-25 | 2005-10-24 | 프로톤 전도성막, 이의 제조 방법 및 이러한 프로톤 전도성막을 사용한 연료 전지 |
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JP2007073310A (ja) * | 2005-09-06 | 2007-03-22 | Sekisui Chem Co Ltd | 膜−電極接合体の製造方法、膜−電極接合体及び固体高分子形燃料電池 |
JP2007512659A (ja) * | 2003-10-10 | 2007-05-17 | バラード パワー システムズ インコーポレイティド | イオン交換膜の伝導性を改良するための水不溶性添加剤 |
WO2007139147A1 (ja) * | 2006-05-31 | 2007-12-06 | University Of Yamanashi | イオン伝導性高分子組成物、その製造方法及びこのイオン伝導性高分子組成物を含む膜並びにこれを用いた電気化学デバイス |
JP2009289747A (ja) * | 2008-05-29 | 2009-12-10 | General Electric Co <Ge> | 高分子電解質膜及び製造方法 |
US8153329B2 (en) * | 2004-06-24 | 2012-04-10 | Konica Minolta Holdings, Inc. | Proton conducting electrolyte membrane and production method thereof and solid polymer fuel cell using the same |
WO2024101081A1 (ja) * | 2022-11-10 | 2024-05-16 | 信越化学工業株式会社 | オルガノポリシロキサンおよびゴム組成物 |
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JP2005314531A (ja) * | 2004-04-28 | 2005-11-10 | Sony Corp | ハイブリッドシリカポリマー、その製造方法およびプロトン伝導性材料 |
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- 2004-04-23 DE DE602004031330T patent/DE602004031330D1/de not_active Expired - Lifetime
- 2004-04-23 CA CA002520827A patent/CA2520827A1/en not_active Abandoned
- 2004-04-23 US US10/554,222 patent/US20060219981A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
JP4769577B2 (ja) | 2011-09-07 |
TWI251368B (en) | 2006-03-11 |
EP1619692B1 (en) | 2011-02-09 |
US20060219981A1 (en) | 2006-10-05 |
TW200501496A (en) | 2005-01-01 |
EP1619692A4 (en) | 2009-12-30 |
JPWO2004097850A1 (ja) | 2006-07-13 |
DE602004031330D1 (de) | 2011-03-24 |
KR20060015529A (ko) | 2006-02-17 |
CA2520827A1 (en) | 2004-11-11 |
KR101214319B1 (ko) | 2012-12-21 |
EP1619692A1 (en) | 2006-01-25 |
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