WO2004019439A1 - 電解質膜とこれを用いた膜電極接合体および燃料電池 - Google Patents
電解質膜とこれを用いた膜電極接合体および燃料電池 Download PDFInfo
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- WO2004019439A1 WO2004019439A1 PCT/JP2003/009368 JP0309368W WO2004019439A1 WO 2004019439 A1 WO2004019439 A1 WO 2004019439A1 JP 0309368 W JP0309368 W JP 0309368W WO 2004019439 A1 WO2004019439 A1 WO 2004019439A1
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- electrolyte membrane
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- film
- base material
- membrane
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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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
-
- 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
-
- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- 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
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to an electrolyte membrane, a membrane electrode assembly using the same, and a fuel cell.
- PEFC also referred to as polymer electrolyte type
- the electrolyte (polymer electrolyte) used for PEFC is generally an electrolyte membrane (PFSA membrane) composed of polyperfluorocarbon sulfonic acid (for example, Nafion (R) manufactured by DuPont Corporation. );).
- PFSA membrane electrolyte membrane
- Nafion (R) Nafion
- DuPont Corporation. DuPont Corporation
- an object of the present invention is to provide an electrolyte membrane having a different configuration from the conventional one, and a membrane electrode assembly (MEA) and a fuel cell using the same.
- MEA membrane electrode assembly
- the electrolyte membrane of the present invention is an electrolyte membrane having ion conductivity, comprising: a base material; and an organic molecule having an ion-exchange group, wherein the organic molecule is chemically bonded to a surface of the base material.
- An organic molecular film is formed, and ions are conducted through the ion exchange groups in the organic molecular film.
- the ion-exchange group is a phosphonyl group, a phosphine group, a sulfol group, a snorefyl group, a carboxyl group, a phosphone group, a phosphine group, a sulfone group, a sulfine group, a mercapto group. It may contain at least one functional group selected from a group, an ether bonding group, a nitro group, a hydroxyl group, a quaternary ammonium group, an amino group and a phosphate group.
- the molecular weight of the organic molecule may be 1000 or less.
- the organic molecule may be chemically bonded to the surface of the base material by a coupling agent.
- the organic molecules may be chemically bonded to an adjacent organic molecule.
- the thickness of the organic molecular film may be in a range of 0.1 nm to 500 nm.
- the organic molecular film may be a monomolecular film.
- the organic molecular film may be a monomolecular accumulation film including a structure in which a plurality of monomolecular films are accumulated.
- the base may have at least one shape selected from particles and fibers, and the electrolyte membrane may include an aggregate of the base.
- the electrolyte membrane further includes a porous membrane, wherein the base material has at least one shape selected from particles and fibers, and the electrolyte membrane includes the base material of the porous membrane. It may include a structure arranged inside the hole.
- the base material may be a folded film.
- the surface of the base material and the membrane surface of the electrolyte membrane may be perpendicular to each other.
- the base material may be wound.
- the base material may be folded in a bellows shape.
- the base material may be a porous membrane.
- the porous membrane has a plurality of through-holes penetrating the porous membrane in a direction perpendicular to the membrane surface, and the organic molecules are chemically bonded to an inner surface of the through-hole.
- the electrolyte membrane of the present invention may be cut in a direction parallel to the membrane surface of the porous membrane. The cross-sectional area of the through-hole may change in the thickness direction of the porous membrane.
- the porous membrane is further formed with a fine hole connected to the through-hole. And both ends of the pore may be open ends. In the electrolyte membrane of the present invention, both ends of the pore may be connected to the through-hole.
- the base material may include at least one material selected from metals, metal oxides, glass, ceramics, clay, carbon, resin and silica.
- the base material is at least one selected from a transition metal oxide, alumina, a fluorine-based resin, an amide resin, a silicone resin, an amide resin, an imide resin and a melamine resin. May contain seed materials.
- the electrolyte membrane of the present invention may include a plurality of the base materials.
- the specific surface area per unit volume of the base material measured by a gas adsorption method may be 100 m 2 Z cm 3 or more.
- ⁇ and d have a relationship expressed by the following equation. May be satisfied.
- a substance is further added on the membrane surface of the organic molecular membrane opposite to the surface bonded to the base material so as to fill a void existing inside the through-hole. It may be arranged.
- the substance may be a water-repellent substance.
- the substance may be a substance obtained by polymerizing at least one material selected from organic substances and inorganic substances.
- a membrane electrode assembly of the present invention includes the electrolyte membrane according to claim 1, a cathode electrode, and an anode electrode, wherein the electrolyte membrane is formed of the force source electrode and the anode electrode. It is located between them.
- a fuel cell according to the present invention includes the electrolyte membrane according to claim 1, a force source electrode, and an anode electrode, wherein the electrolyte membrane is sandwiched by the anode electrode and the cathode electrode.
- a fuel supply unit that supplies a fuel to the anode electrode; and an oxidant supply unit that supplies an oxidant to the cathode electrode.
- the fuel may include at least one kind of gas or liquid selected from hydrogen and hydrocarbon.
- the fuel may include methanol.
- FIG. 1 is a schematic diagram showing one example of the electrolyte membrane of the present invention.
- FIG. 2 is a diagram illustrating an example of the state of organic molecules in the electrolyte membrane of the present invention.
- FIGS. 3A to 3C are diagrams for explaining an example of the organic molecules used in the electrolyte membrane of the present invention.
- FIG. 4 is a schematic view showing another example of the electrolyte membrane of the present invention.
- FIG. 5 is a schematic diagram showing another example of the electrolyte membrane of the present invention.
- FIGS 6A to 6C are schematic diagrams showing still another example of the electrolyte membrane of the present invention.
- FIG. 7A and 7B are schematic diagrams showing another example of the electrolyte membrane of the present invention.
- FIG. 8 is a schematic diagram showing another example of the electrolyte membrane of the present invention.
- FIG. 9 is a schematic diagram showing another example of the electrolyte membrane of the present invention.
- FIG. 10 is a schematic view showing another example of the electrolyte membrane of the present invention, which is different from the above.
- FIG. 11 is a schematic view showing another example of the electrolyte membrane of the present invention, which is different from the above.
- FIG. 13 is a schematic diagram showing another example of the electrolyte membrane of the present invention.
- FIG. 13 is a schematic diagram showing another example of the electrolyte membrane of the present invention.
- FIG. 14 is a schematic diagram illustrating an example of a model of a base material having a through hole.
- FIG. 15 is a schematic diagram for explaining another example of the electrolyte membrane of the present invention.
- FIGS. 16A to 16C are schematic process diagrams illustrating an example of the method for producing an electrolyte membrane of the present invention.
- FIG. 17 is a schematic diagram illustrating an example of the membrane / electrode assembly of the present invention.
- FIG. 18 is a schematic diagram showing one example of the fuel cell of the present invention.
- FIG. 19 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 20 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 21 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 22 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 23 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 24 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 25 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 26 is a diagram for explaining the organic molecules used in the example.
- FIG. 27 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 28 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 29 is a diagram for explaining the organic molecular film formed in the example.
- FIG. 30 is a diagram for explaining the precursor used in the examples. Embodiment of the Invention
- FIG. 1 is a schematic diagram showing one example of the electrolyte membrane of the present invention.
- the dissolving membrane 1 is an electrolyte membrane having ion conductivity, and includes a substrate 2 and organic molecules having an ion exchange group.
- the organic molecules are chemically bonded to the surface of the base material 2 to form the organic molecular film 3, and ions are conducted through ion exchange groups in the organic molecular film 3.
- the electrolyte membrane 1 includes a base material 2 in which a through-hole connecting both membrane surfaces (one main surface and the other main surface) of the electrolyte membrane 1 is formed. I have. Further, the organic molecules are chemically bonded to the inner surface of the through hole to form the organic molecular film 3.
- the electrolyte membrane of the present invention is not limited to such a configuration.
- Other configurations for example, variations in the shape of the base material 2 will be described later.
- hatches are omitted for easy understanding.
- hatches may be omitted in the following drawings.
- an electrolyte membrane having a configuration different from that of a conventional one can be obtained. Further, an electrolyte membrane having excellent ionic conductivity (ion conductivity) can be obtained. Further, since it is not always necessary to use a fluorinated polymer, it is possible to use a lower cost electrolyte membrane as compared with a conventional PTFE membrane. In addition, by including a base material, an electrolyte membrane having excellent strength, Z or moldability can be obtained. These effects are selective, and the electrolyte membrane of the present invention does not necessarily have to satisfy these effects simultaneously. These effects can be selected by selecting the type of organic molecules contained in the electrolyte membrane, the shape of the organic molecular film, the shape of the substrate, and the material.
- the ions are conducted by the ion exchange group of the organic molecule.
- the direction in which ions are conducted as a whole through the inside of the electrolyte membrane is not particularly limited. What is necessary is just to set arbitrarily according to the characteristic required as an electrolyte membrane, and it can set by selecting the shape of a base material, the kind of an organic molecule, the shape of an organic molecular film, etc.
- the ions The direction of conduction is, for example, the direction connecting both membrane surfaces of the electrolyte membrane.
- the direction may be the direction of arrow A shown in FIG.
- the type of ions to be conducted is not particularly limited. It can be set arbitrarily by selecting the ion exchange group of the organic molecule.
- the ion-exchange groups are a phosphonyl group (—HPO), a phosphiel group (_H 2 PO), a sulfonyl group (_SO 2 ⁇ ), a sulfinyl group (1 S O_), Karubokishinore group (one COOH), phosphonic group (an P_ ⁇ (OH) 2), Fosufi down group (an HP O (OH)), sulfone group (- SO a H), Surufi down group (- SO 2 H ), mercapto group (_ SH), ether bond group (one O-), nitro group (-N0 2), a hydroxyl group (_OH), quaternary Anmoniumu group (an NH 4 +), amino group (one NH 2) and also it may contain one functional group less selected from
- a phosphiel group, a carboxyl group, and a sulfone group are preferred.
- an electrolyte membrane that conducts hydrogen ions (H +) well can be obtained. Therefore, it can be used for fuel cells instead of the polymer electrolyte membrane generally used for PEFC. Further, it can be used for electrochemical devices such as various gas sensors, electrochemical capacitors, secondary batteries, and primary batteries by utilizing hydrogen ion conductivity. Further, since it has a high ion exchange capacity, it can be used for ion exchange membranes, acid catalysts, and the like.
- an ion exchange group may be arranged at the terminal of the main chain of the organic molecule, or may be arranged near the center of the main chain.
- an ion exchange group may be arranged in the side chain of the organic molecule or at the end of the side chain. For example, placing an ion-exchange group near the center of the main chain or near the side chain further frees up organic molecules. Since it can be laminated (accumulated) on the surface, an electrolyte membrane containing many ion-exchange groups can be obtained.
- the molecular weight of the organic molecule may be 1000 or less. Especially, the molecular weight is preferably 500 or less, more preferably 100 or less. In other words, it is preferable to use a monomer or a laminate of, for example, about several to several + layers of a monomer, rather than a polymer.
- the degree of freedom in the shape of the base material is improved, and / or the ionic conductivity is improved. And Z and / or fuel crossover can be suppressed.
- the molecular weight may be, for example, a weight average molecular weight.
- the lower limit of the molecular weight of the organic molecule is not particularly limited, but may be, for example, 17 or more.
- the molecular length of the organic molecule is not particularly limited. It is sufficient if it is in the range of -500 nm, preferably in the range of 0.1 nm to 2 nm. It is considered that such organic molecules can be arranged more uniformly on the surface of the substrate. Therefore, an electrolyte membrane having more excellent ionic conductivity can be obtained.
- the chemical bond in the electrolyte membrane of the present invention is not particularly limited, and may be, for example, at least one bond selected from a covalent bond, an ionic bond, a coordinate bond, a metal bond, and a hydrogen bond.
- the organic molecule may form a covalent bond with the surface of the substrate that has or is provided with active hydrogen.
- the chemical bond is a covalent bond formed by an elimination reaction, Or a bond via an oxygen atom.
- a bond can be formed when a coupling agent is used for an organic molecule or when a combination of an organic molecule and a coupling agent is used.
- the organic molecule may be chemically bonded to the surface of the substrate by the coupling agent.
- the coupling agent is not particularly limited, and may be, for example, a silane coupling agent whose terminal group contains at least one selected from chlorosilane, methoxysilane and ethoxysilane.
- the main chain portion may be a linear alkyl group or a fluoroalkyl group. When the main chain is a linear alkyl group, the number of carbon atoms is, for example, in the range of 2 to 50, preferably in the range of 8 to 20.
- the molecular length of the silane coupling agent is, for example, in the range of 0.5 nm to 3.8 nm.
- an organic molecular film in which organic molecules are more uniformly arranged can be formed. Therefore, an electrolyte membrane having more excellent properties such as ion conductivity can be obtained.
- the organic molecule and the coupling agent may be the same molecule. That is, for example, the organic molecule may have an ion-exchange group as described above while the terminal group of the organic molecule is a silane group as described above. Further, the organic molecule may not have an ion exchange group from the beginning, and may have an ion exchange group after being chemically bonded to the surface of the substrate. That is, an organic molecule having no ion exchange group may be chemically bonded to the surface of the substrate, and then the organic molecule may be provided with an ion exchange group.
- FIG. 2 is a schematic diagram in which the surface of the base material of such an electrolyte membrane is enlarged.
- the organic molecular film 3 shown in FIG. 2 includes organic molecules 4, 4a and 4b having ion exchange groups, a and the organic molecule 4 b adjacent to the organic molecule 4 a are chemically bonded. With such a structure, the organic molecular film 3 having excellent durability against hydrolysis and oxidation can be obtained. Further, the organic molecular film 3 in which the ion exchange groups are more uniformly arranged can be obtained.
- the bond between adjacent organic molecules may be a bond via a side chain of the organic molecule.
- the side chain may include an alkyl group in which a part or all of hydrogen is substituted by fluorine.
- the organic molecular film 3 having higher durability can be obtained.
- the thickness of the organic molecular film is not particularly limited, and is, for example, in a range from 0.1 nm to 500 nm. Among them, the range is preferably from 0.1 nm to 2 nm, and particularly preferably from 0.3 nm to 1 nm.
- the thickness of the organic molecular film can be controlled by, for example, adjusting the molecular length of the organic molecule, the cumulative number of organic molecules, and the like.
- the organic molecular film may be a monomolecular film. Since ion exchange groups can be arranged almost uniformly, an electrolyte membrane having more excellent properties such as ion conductivity can be obtained. Further, a monomolecular film containing an ion exchange group may be further laminated on the organic molecular film.
- the electrolyte membrane of the present invention for example, organic molecules, SH group in the molecule, S i X n Y m group (wherein, X is at one least selected from halogen and no more than 8 alkoxy group having a carbon Y is at least one selected from an aromatic ring substituent having at least one hydrocarbon group having 8 or less carbon atoms, a hydrogen atom, a hydrocarbon group having 8 or less carbon atoms, and a phenyl group.
- a i to A 6 are one (CH 2 ) s COOH (s is an integer in the range of 0 to 3), one (CH 2 ) t OH (t is an integer in the range of 0 to 3), And (CH 2 ) U NVW (u is an integer in the range of 0 to 2, and V and W are each independently an aromatic ring substituted with at least one hydrocarbon group having 8 or less carbon atoms.
- the base material is a metal
- a metal bond may be formed between the base material and the s atom, or the base material may be coordinated with the metal.
- a bond may be formed.
- a siloxane bond may be formed with active hydrogen on the surface of the substrate.
- the binding group is a silane group was described, but the same applies to Ti, Ge, Sn, Zr, Hf, and the like in addition to Si. .
- other bonds may be formed between the substrate and the organic molecules.
- the substrate in the electrolyte membrane of the present invention will be described.
- the shape, material, structure, and the like of the substrate in the electrolyte membrane of the present invention are not particularly limited as long as a chemical bond can be formed with the above-described organic molecule on the surface.
- an electrolyte membrane when used in a fuel cell, it must be electrically insulated because it is insoluble in fuel, water, and weak acids such as formic acid and acetic acid, which are considered as by-products during power generation.
- the term “electrically insulated” means that the base material as a whole may be insulated. For example, in the case of a base material made of metal, it is sufficient that the surface of the base material is insulated with a metal oxide or resin.
- the substrate may include at least one material selected from metals, metal oxides, glasses, ceramics, clays, cements, resins and silicas. More specific examples include transition metal oxides, alumina, fluorine-based resins, amide resins, silicone resins, amide resins, and imide resins. And at least one material selected from melamine resins. These materials may be arbitrarily set according to the characteristics required for the electrolyte membrane, the shape of the electrolyte membrane, the type of organic molecules, and the like. When a porous substrate is required, for example, silica gel, zeolite, titania, alumina, etc. Is also good. In addition, the material of the base material may be described later depending on the shape of the base material.
- the surface of the substrate may be surface-treated.
- the surface treatment may be any chemical treatment or physical treatment. More specifically, for example,
- Any treatment that promotes activation of the substrate surface such as oxidation, reduction, formation of specific groups, and change in wettability (change in surface energy) may be used.
- a treatment for inactivating the surface of the base material such as a fluorination treatment may be performed.
- FIG. 4 shows an example of the electrolyte membrane of the present invention.
- the base material 2 is in the form of particles, and the electrolyte membrane 1 includes such an aggregate of the base material 2.
- Such an electrolyte membrane may be formed, for example, by forming an organic molecular film 3 on the surface of the base material 2 and then forming the film into a film by pressure molding or the like. Further, for example, the organic molecular film 3 may be formed on the surface of the substrate 2 after the substrate 2 is formed into a film by pressure molding or the like.
- an inorganic or organic binder may be mixed, or the organic molecular membranes 3 formed on the surface of the substrate 2 may be bonded to each other.
- the substrate 2 may be in the form of a fiber, in addition to the particle shown in FIG. 4, or a mixture of the fibrous base and the particulate base may be used.
- FIG. 4 shows a partially enlarged region B of the electrolyte membrane 1. (The same applies to region C in Fig. 5)
- the substrate 2 itself may be porous.
- An organic molecular film can also be formed inside the substrate 2.
- FIG. 5 shows another example of the electrolyte membrane of the present invention.
- the electrolyte membrane 1 shown in FIG. 5 further includes a porous membrane 5, and the substrate 2 has at least one shape selected from particles and fibers. Further, the electrolyte membrane 1 has a structure in which the base material 2 is arranged inside the pores of the porous membrane 5.
- the average particle size is not particularly limited. For example, 0.02 ⁇ ! It may be in the range of up to 20 m.
- the shape of the particles is not particularly limited.
- the substrate is fibrous, its size and the like are not particularly limited.
- the substrate may be in the form of a folded film.
- an electrolyte membrane can be obtained without using a porous membrane as described above.
- the substrate itself does not necessarily need to be a porous film.
- the production process can be simplified, and a lower-cost electrolyte membrane can be obtained.
- the film thickness can be freely set, an electrolyte membrane having excellent strength can be obtained.
- the distance between the substrates can be set to about 5 nm to 50 nm, it is possible to use an electrolyte membrane in which fuel crossover is suppressed.
- the thickness of the electrolyte membrane can be, for example, about 0.2 mm.
- the electrolyte membrane 1 shown in FIGS. 6A and 6B is an electrolyte membrane 1 having ion conductivity, and includes a wound film-shaped substrate 2 and organic molecules having ion exchange groups. .
- the organic molecules are chemically bonded to the surface of the substrate 2 to form the organic molecular film 3.
- the ion can be conducted in a direction parallel to the surface of the substrate 2 (for example, in the direction of the arrow shown in FIG. 6A).
- FIG. 6B is a schematic view of the electrolyte membrane 1 shown in FIG. 6A as viewed from above.
- 6A and 6B are schematic diagrams in which a part of the electrolyte membrane is enlarged in order to explain a state in which the substrate 2 is folded.
- the electrolyte membrane 1 has, for example, a shape as shown in FIG. 6C, and an enlarged view of a part (dotted line) of the electrolyte membrane 1 shown in FIG. 6C corresponds to FIGS. 6A and 6B.
- Do 6A and 6B (the long side of the strip-shaped substrate 2) corresponds to a part of the membrane surface 4 of the electrolyte membrane 1 shown in FIG. 6C.
- FIGS. 7A and 7B described below are also schematic diagrams in which a part of the electrolyte membrane of the present invention is enlarged, and the long side portion of the strip-shaped base material 2 is the electrolyte membrane 1 Corresponds to a part of the film surface.
- FIGS. 7A and 7B show another example of a film-like electrolyte membrane in which the substrate is folded.
- the base material 2 is folded in a bellows shape.
- An organic molecular film 3 is formed on the substrate 2 in the same manner as the examples shown in FIGS. 6A to 6C, and is formed on the surface of the substrate 2 via the ion exchange group in the organic molecular film 3. Ions can be conducted in parallel directions (for example, in the direction of the arrow shown in FIG. 7A).
- FIG. 7B is a schematic diagram of the electrolyte membrane 1 shown in FIG. 7A as viewed from above.
- the direction in which ions are conducted is parallel to the membrane surface of the organic molecular membrane. For this reason, by using the electrolyte membrane 1 as shown in FIGS. 6A to 6C and FIGS. 7A to 7B, the direction in which ions are conducted is set to the direction perpendicular to the membrane surface of the electrolyte membrane ( 6A and 7A). At this time, the ionic conductivity of the electrolyte membrane can be maximized.
- the surface of the substrate and the membrane surface of the electrolyte membrane May be perpendicular to each other.
- the direction in which ions are conducted can be set to a direction perpendicular to the membrane surface of the electrolyte membrane, so that the ionic conductivity of the electrolyte membrane can be maximized.
- the material used for the film-shaped substrate is not particularly limited as long as the material can be formed into a film.
- a polymer material such as a resin or an inorganic material such as a metal oxide may be used.
- a composite material of at least one inorganic material selected from glass, silica, alumina, and titania and a polymer material is preferable from the viewpoint of strength and the like.
- a base material having a multilayer structure in which a film made of a polymer material is used as a base and the inorganic material layer is formed on the surface thereof may be used. In this way, when the inorganic material layer is formed on the surface, the organic molecular film can be more easily formed on the surface of the base material.
- the thickness of the film-shaped substrate is not particularly limited. To 100 m, preferably in the range of 0.1 ⁇ m to 1 ⁇ m.
- the substrate may be a porous film or a non-porous film. In the case of a non-porous film, the conduction of ions in the thickness direction of the substrate can be suppressed. Therefore, for example, if the electrolyte membrane 1 as shown in FIGS. 6A to 6C and FIGS. 7A to 7B is used, ions can be conducted only in a direction perpendicular to the membrane surface of the electrolyte membrane. Thus, an electrolyte membrane having more excellent ionic conductivity can be obtained.
- the method of folding the film-shaped base material is not particularly limited.
- the base material may be wound as shown in FIGS. 6A to 6C, or the base material may be folded in a bellows shape as shown in FIGS. 7A to 7B. What is necessary is just to set arbitrarily according to the characteristic required as an electrolyte membrane.
- a core made of metal, glass, or the like may be prepared, and the substrate may be wound around the core.
- the shape of the cross section of the core used is not particularly limited. For example, a circular, elliptical, or polygonal shape may be used.
- the core may be removed after the base material is wound, or may not be removed.
- an electrolyte having ionic conductivity may be disposed in the portion where the core was present.
- a different material from the organic molecular film may be used for the electrolyte to be disposed at this time.
- the substrate may be wound from the beginning without using the core (for example, in the example shown in FIGS. 6A to 6C, the substrate 2 is wound without using the core. Yes)
- the base material is folded, the length of the folded base material may be uniform throughout or may be non-uniform.
- the interval between the folded film-shaped substrates is not particularly limited. For example, it is in the range of 5 nm to 50 ⁇ m, preferably in the range of 5] 111 to 10111111. Since the distance between the substrates can be on the order of several nm, it is possible to use an electrolyte membrane in which crossover of fuel or the like is suppressed.
- the organic molecular film may be formed only on one main surface of the film-shaped base material, or may be formed on both the front and back main surfaces. When the organic molecular film is formed on both surfaces of the substrate, the ionic conductivity of the electrolyte film can be further improved.
- the electrolyte membrane in which the base material is a folded film can have a large thickness, and various materials such as a composite material of an inorganic material and a polymer material are used for the base material. be able to. Further, the substrate may be non-porous. Therefore, an electrolyte membrane having higher strength can be obtained. For example, when incorporated into a fuel cell, an electrolyte membrane having excellent strength that can withstand variations in cell clamping pressure and the like can be obtained.
- the substrate may be a porous membrane.
- a porous membrane has multiple penetrations that penetrate the porous membrane in a direction perpendicular to the membrane surface.
- a through hole is formed, and the organic molecule is chemically bonded to the inner surface of the through hole to form an organic molecular film.
- the cross-sectional area of the through hole cut in a direction parallel to the film surface of the porous film changes in the thickness direction of the porous film.
- FIG. 8 shows an example of such an electrolyte membrane.
- the electrolyte membrane 1 shown in FIG. 8 includes a base material 2 which is a porous membrane and an organic molecule having an ion exchange group.
- a plurality of through holes penetrating the porous membrane in a direction perpendicular to the membrane surface are formed in the porous membrane (base material 2).
- the organic molecules are chemically bonded to the inner surface of the through-hole to form an organic molecular film 3, and the cross-sectional area of the through-hole cut in a direction parallel to the film surface of the porous film is It changes in the thickness direction.
- the “cross-sectional area of the through-hole” in the present specification refers to a cross-sectional area of a surface obtained by cutting the through-hole in a direction parallel to the membrane surface of the porous membrane or the electrolyte membrane 1.
- an electrolyte membrane 1 since the organic molecular membrane 3 is formed in a direction perpendicular to the membrane surface, an ion conduction path is formed in a direction perpendicular to the membrane surface, and an electrolyte membrane having excellent ion conductivity is obtained. can do. Further, the cross-sectional area of the through-hole changes in the thickness direction of the porous membrane. That is, since the through-hole is provided with a relatively large area and a relatively small area, The electrolyte membrane 1 is excellent in conductivity and in which fuel crossover is suppressed.
- the size of the gap (for example, the inside diameter of the gap, the cross-sectional area, etc.) existing inside the through-hole can be reduced, that is, fuel crossover can be suppressed.
- the ion exchange groups can be uniformly arranged inside the organic molecular film 3, that is, the ionic conductivity can be improved.
- such an electrolyte membrane is obtained, for example, by laminating a plurality of porous membranes having different through-hole cross-sectional areas. Can be. Further, for example, it can also be obtained by forming an electrolyte membrane in which particulate base materials are aggregated. For example, the density of the particulate base material may be changed in the thickness direction of the electrolyte membrane.
- the gap existing inside the through hole will be described.
- an electrolyte membrane is used in which a through-hole of a porous membrane having an through-hole is filled with an organic substance and / or an inorganic substance, a minute gap may remain inside the through-hole. It is considered that fuel moves through such a gap extending in a direction perpendicular to the membrane surface of the electrolyte membrane. Therefore, in order to provide an electrolyte membrane that can suppress fuel crossover, it is necessary to minimize the size of the fine gaps existing in the through holes (in the present specification, such fine gaps are used). Are called "gap").
- the cross-sectional area of the through hole may change gradually or may change stepwise.
- the characteristics of the electrolyte membrane can be more easily controlled by changing the ratio of each of a relatively large area and a relatively small area to the through hole. be able to. For example, by increasing the proportion of a region having a relatively large cross-sectional area, an electrolyte membrane having better ionic conductivity can be obtained.
- the cross-sectional area of the through hole may be the smallest near the center in the thickness direction of the porous membrane (for example, the electrolyte membrane 1 shown in FIGS. 8 and 9). . Further, the cross-sectional area of the through-hole may be gradually reduced from the surface of the porous film to the vicinity of the center in the thickness direction of the porous film (for example, the electrolyte film 1 shown in FIG. 9). Further, the cross-sectional area of the through-hole may be the smallest on the membrane surface of the porous membrane (for example, the electrolyte membrane 1 shown in FIGS. 10 and 11).
- the cross-sectional area of the through-hole may gradually increase from the surface of the porous film to the vicinity of the center in the thickness direction of the porous film (for example, the electrolyte film 1 shown in FIG. 10). ). Further, the cross-sectional area of the through-hole may be gradually increased from one membrane surface of the porous membrane to the other membrane surface (for example, the electrolyte membrane 1 shown in FIG. 11). value, for example, may be in the range of 3 nm 2 ⁇ 3 0 0 nm 2, preferably in the range of 3 nm 2 ⁇ 1 0 nm 2 . In such an electrolyte membrane, the size of the gap existing inside the through hole can be further reduced. That is, an electrolyte membrane in which fuel crossover is further suppressed can be obtained.
- the minimum value S m i n of the cross-sectional area of the through hole the ratio between the maximum value S max of the cross-sectional area of the through-holes (i.e., S ma x / S min), for example, 1 may be two or more , Preferably 3 or more.
- ion exchange groups can be more uniformly arranged inside the organic molecular membrane.
- the minimum value of the cross-sectional area of each gap present inside the through-hole may be, for example, 10 nm 2 or less, and preferably 5 nm 2 or less. Since it is considered that the fuel crossover occurs through a gap existing inside the through-hole, the electrolyte membrane can further suppress the fuel crossover. If the fuel Ru with methanol, the projected area of the methanol was calculated from the molecular size is about 0. 1 4 rim 2, into the small category among the organic fuel used in a fuel cell. The minimum value is much larger than the value of 0.14 nm 2 . However, in reality, the inside of the gap is covered with a large number of ion-exchange groups, and it is thought that a fixed layer is formed by dissociated hydrogen ions and its hydration water. It is thought that the situation can be further reduced.
- the area where the cross-sectional area of the through hole is the smallest is, for example, the area 51 in the electrolyte membrane 1 shown in FIG. Also, for example, the electrolyte membrane shown in FIG. In FIG. 1, the region 52 near the center in the thickness direction of the porous membrane is shown, and in the electrolyte membrane 1 shown in FIGS. 10 and 11, the regions 53 and 54 near the porous membrane surface are shown. Is shown. As shown in FIGS. 9 to 11, in an electrolyte membrane in which the cross-sectional area of the through-hole is gradually changed, the length of these regions in the direction perpendicular to the surface of the porous membrane is, for example, The thickness may be in the range of 10% to 50% with respect to the thickness of the porous film.
- the material used for the porous membrane for example, at least one material selected from glass, silica, alumina, and titania may be used.
- the inner surface of the through hole may be coated with the above-mentioned inorganic material.
- the ratio of the through holes in the porous membrane is, for example, 10 volumes in terms of porosity. /. ⁇ 60 volumes. /. It is sufficient if it is within the range.
- a hole may exist in the porous film in addition to the above-mentioned through hole.
- the thickness of the porous membrane may be, for example, any thickness required for the electrolyte membrane, for example, 5! ⁇ Lmm m.
- the area of the porous membrane may be, for example, an area necessary for forming a fuel cell.
- FIG. 12 shows another example of the electrolyte membrane of the present invention.
- the electrolyte membrane 1 shown in FIG. 12 is an electrolyte membrane 1 having ion conductivity and includes a base material 2 which is a porous membrane and organic molecules having ion exchange groups.
- the porous membrane has a plurality of through holes penetrating the porous membrane in a direction perpendicular to the membrane surface, and pores 7 connected to the through holes. Both ends of the pore 7 are open ends.
- the organic molecules are chemically bonded to the inner surface of the through-hole to form the organic molecular film 3.
- ions can be transferred from one membrane surface to the other membrane surface via the organic molecular membrane 3 containing an organic molecule having an ion exchange group. That is, the electrolyte membrane 1 having ion conductivity can be obtained.
- the organic molecular film 3 is formed in a direction perpendicular to the film surface, an ion conduction path is formed in a direction perpendicular to the film surface, so that an electrolyte film having excellent ion conductivity can be obtained. Furthermore, the formation of the pores 7 connected to the through-holes and having open ends at both ends makes it possible to make the organic molecular film 3 inside the through-holes more uniform and to have more excellent characteristics. (For example, it is more excellent in ion conductivity and can further suppress fuel crossover.)
- the electrolyte membrane 1 can be used.
- the pore 7 can also serve as a buffer for the by-product. Therefore, the organic molecular film 3 inside the through hole can be made more uniform.
- the shape of the pores 7 is not particularly limited. Further, (cross-sectional area taken along a plane perpendicular to the pore 7 force S extending direction) cross-sectional area of the aperture 7, for example, 3 nm 2 - may be in the range of 2 0 0 0 nm 2, 3 The range of nm 2 to 20 nm 2 is preferred.
- the cross-sectional area of the pores 7 is preferably smaller than the cross-sectional area of the through-hole.
- the direction in which the pores 7 extend is not particularly limited. For example, the connection is not necessarily required to be perpendicular to the through hole, but may be at any angle. Further, both ends of the pore 7 may be connected to the through-hole.
- the connecting through-holes may be the same or different.
- one end of the pore 7 may be connected to the through-hole, and the other end of the pore 7 may be connected to the membrane surface of the porous membrane (that is, the electrolyte membrane 1) (for example, The pore 7a shown in Figure 13).
- the electrolyte membrane 1 for example, The pore 7a shown in Figure 13.
- the shape of the porous membrane is not particularly limited as long as the through-holes and the pores 7 are formed.
- a film formed by assembling flat plates in this case, for example, the flat plate may be porous, or a gap formed between the flat plates may be a through hole Or a film formed by assembling particles (for example, a gap formed between particles may be formed as a through hole or a pore).
- the electrolyte membrane of the present invention does not have to include one substrate, and may include a plurality of substrates.
- the base material is a folded film
- an aggregate in which a plurality of base materials are laminated may be folded, or a plurality of folded base materials may be assembled to form an electrolyte membrane.
- the cross-sectional area of the through-holes increases in the thickness direction of the porous film. It can also be a changing electrolyte membrane.
- the specific surface area per unit volume of the base material measured by the gas adsorption method may be 100 m 2 / cm 3 or more, or 200 m 2 / cm 3 or more. Is preferred. It is believed that the larger the surface area of the substrate, the more organic molecules can bind to the substrate. Therefore, an electrolyte membrane having more excellent ion conductivity can be obtained.
- the upper limit of the specific surface area is not particularly limited, but may be, for example, about 100 m 2 Zcm 3 .
- the method for measuring the specific surface area by the gas adsorption method is not particularly limited, and a general method may be used.
- a measurement condition when a nitrogen adsorption method is used as a gas adsorption method, for example, an analysis based on the BET theory may be performed after measuring a nitrogen adsorption isotherm.
- ⁇ and d are represented by the formula (4X ⁇ ) Zd> 1
- the relationship indicated by 0 may be satisfied.
- the value represented by the above equation is a value corresponding to the specific surface area of the substrate. Therefore, when ⁇ and d satisfy the above expression, an electrolyte membrane having more excellent ion conductivity can be obtained.
- the upper limit of the above equation is not particularly limited, but may be, for example, 300.
- the shape of the porous film can be considered using a model as shown in FIG.
- the average pore diameter of the through-holes having a certain distribution in the actual porous membrane is represented by one average value, and there are a plurality of through-holes having the average pore diameters of the above average value.
- the through-hole of the porous membrane The shape can be described by the following parameters.
- Base material 2 porous membrane area S (cm 2 ), base material 2 thickness ⁇ (cm), base material porosity ⁇ (volume%), average pore diameter d (nm), penetration
- the average curvature of the hole is defined as a value obtained by dividing the average penetration length of the through-hole in the membrane penetration direction by the thickness of the base material.
- the volume occupied by one through hole is expressed by the following equation (1).
- the volume occupied by the entire through hole is represented by the following equation (2).
- the number ⁇ of through holes present in the substrate having the area S is represented by the following equation (3).
- the total surface area of the base material can be roughly considered as the total surface area of the through holes.Therefore, the total surface area of the base material can be obtained by multiplying the surface area of one through hole by the number of through holes. it can.
- the surface area of one through hole is represented by the following equation (4).
- the total surface area of the substrate is represented by the following equation (5).
- Equation (5) / (S X 1) (4 X ⁇ ) Zd
- the porosity of the base material is ⁇ (volume%) and the average curvature of the poor hole is ⁇
- ⁇ and ⁇ are expressed by the following equation: ⁇ no ⁇ 2
- the relationship shown in 20 may be satisfied.
- the value shown in the above equation is the fuel crossover It is a value corresponding to one quantity. For this reason, when ⁇ and ⁇ satisfy the above expression, it is possible to obtain an electrolyte membrane in which fuel crossover is further suppressed.
- the lower limit of the above equation is not particularly limited, but may be, for example, 0.001.
- electrolyte membrane of the present invention a substance is further arranged on the membrane surface of the organic molecular membrane opposite to the surface bonded to the base material so as to fill a gap existing inside the through-hole. Is also good. An electrolyte membrane in which fuel crossover is further suppressed can be obtained.
- the type of the substance 9 is not particularly limited.
- it may be a water-repellent substance.
- the fuel is a hydrophilic fuel such as methanol or an aqueous methanol solution, crossover of the fuel can be more efficiently suppressed.
- the water-repellent substance for example, a polymer of a hydrocarbon molecule, or a substance partially substituted with fluorine may be used.
- the substance 9 may be a substance obtained by polymerizing at least one material selected from organic substances and inorganic substances. Such a substance can be obtained, for example, by filling a gap remaining inside the through-hole with a precursor of the substance and polymerizing the precursor.
- the precursor has a smaller molecular weight (for example, the precursor is not limited to a solid, but may be a liquid or a gas), so that the substance is efficiently filled in the gaps existing in the through holes. can do. For this reason, it is necessary to make the inside of the through hole more dense. Can be.
- organic substance for example, styrene, dibutylbenzene, methyl methacrylate, or a substance in which a part thereof is substituted with fluorine may be used.
- inorganic substance for example, tetramethoxysilane, tetraethoxysilane, 3-glycidoxypropyl biltrimethoxysilane, which is a silane compound having an organic group, may be used.
- the polymerization method is not particularly limited, and examples thereof include a sol-gel method, a radical reaction polymerization, an anion reaction polymerization, a cation reaction polymerization, a living reaction polymerization, a catalyst reaction polymerization, a condensation reaction polymerization, a ring opening reaction, and a thermal polymerization.
- a simple method may be used.
- it is preferable that one end of the molecule is bonded to the base material from the viewpoint of stability and durability from the viewpoint of stability and durability. At this time, the one end may be directly bonded to the base material, or may be bonded via an organic molecular film (the organic molecule in the organic molecular film may be bonded to the one end). .
- the manufacturing method shown in FIGS. 16A to 16C is a method for manufacturing the electrolyte membrane shown in FIG.
- the first film formed in the step (i) is not particularly limited as long as a porous film having a through-hole formed in a direction perpendicular to the film surface can be formed in the step (ii).
- a first film made of the same material as the porous film (that is, the porous film included in the electrolyte film) formed in the step (ii) may be formed.
- a method for forming the first film is not particularly limited, and a general film forming method may be used.
- the film formation method may be selected depending on the material used for the first film, and for example, a PVD method such as a sputtering method, a CVD method, a sol-gel method, or the like may be used.
- the first film may be formed on a substrate.
- a substrate for example, a metal substrate such as Si, Ni, or A1, a semiconductor substrate, or a ceramic substrate such as silica or alumina may be used. Further, the substrate may be a porous substrate. In this case, in step (iii) above, the bonding of the organic molecules can be performed more easily.
- the separation of the substrate and the first film is performed at any time. It is good. Also, the two need not be separated.
- the step of forming a through-hole penetrating the first film in a direction perpendicular to the film surface of the first film is not particularly limited.
- the first film formed in the step (i) is made of an amorphous material containing at least one element selected from Si and Ti, Fe, and O;
- the composition ratio between the seed element and Fe may vary in the thickness direction of the first film.
- the composition ratio, the cross-sectional area, porosity, and the like of the through hole formed in the step (ii) can be controlled.
- Fe By increasing the composition ratio, the cross-sectional area of the through-hole can be increased. Conversely, by increasing the composition ratio of Fe, the cross-sectional area of the through hole can be reduced.
- a porous film made of at least one material selected from silica and titanium can be obtained.
- the method for forming the first film in which the above composition ratio changes in the thickness direction is not particularly limited.
- sputtering may be performed using two types of targets (for example, one target is a target containing at least one of the above elements, and the other target is a target containing Fe).
- the step (ii) comprises: (a) heat-treating the first film, thereby forming an oxide of at least one element and a film surface of the first film. (B) removing the Fe oxide to form a porous film in which a through-hole is formed in a direction perpendicular to the film surface; And a step of forming
- the cross-sectional area of the through hole to be formed, the porosity, and the like can be controlled according to the composition ratio set in the step (i). More specifically, the cross-sectional area of the through-hole can be increased by increasing the composition of Fe.
- the temperature of the heat treatment is not particularly limited.
- the temperature is in the range of 400 ° C. to 800 ° C.
- the heat treatment may be performed in an atmosphere containing oxygen such as air, and the time of the heat treatment is, for example, in a range of 60 min to 600 min.
- S i and F e are used, phase separation into S i O 2 and F e O occurs.
- the method of removing the oxide of Fe in the step (b) is not particularly limited. For example, removing the whole by immersing it in an acidic aqueous solution 3 009368
- the acidic aqueous solution for example, a solution in which hydrochloric acid is diluted with water may be used.
- the method of chemically bonding an organic molecule having an ion-exchange group on the inner surface of the through-hole is not particularly limited.
- a silane coupling agent may be used.
- the porous film formed in step (ii) may be immersed in a solution containing a silane coupling agent, and then immersed in a solution containing organic molecules. .
- the above-described ion exchange group, organic molecule, and silane coupling agent may be used as the ion exchange group, the organic molecule, and the silane coupling agent.
- the organic molecule itself contains a silane group it is only necessary to immerse the porous film in a solution containing organic molecules, so that an electrolyte membrane can be obtained with higher productivity.
- the cross-sectional area of the through-hole is freely changed in the thickness direction of the porous film. Can be done. For example, it can be changed stepwise or gradually. In the case where a through-hole having a gradually changing cross-sectional area is formed, organic molecules can be uniformly bonded in the step (iii).
- the portion in the thickness direction of the porous film in which the portion having the smallest cross-sectional area of the through hole is arranged can be freely set.
- the cross-sectional area of the through-hole may be smallest near the center in the thickness direction of the porous film.
- these solutions are considered to react from the vicinity of the surface of the porous film. Therefore, the larger the cross-sectional area of the through hole near the surface of the porous film, the higher the reactivity can be.
- the cross-sectional area of the through-hole may gradually increase from the surface of the porous film to the vicinity of the center in the thickness direction of the porous film.
- a porous film made of an inorganic material has the weakest surface portion against bending and pressure. Therefore, in this case, the strength of the porous film can be further improved.
- the cross-sectional area of the through-hole may be gradually increased from one film surface of the porous film to the other film surface.
- the film having the larger cross-sectional area may be immersed in a solution containing a silane coupling agent or an organic molecule.
- the MEA 11 shown in FIG. 17 includes the above-mentioned electrolyte membrane 1 of the present invention, a cathode electrode 12, and an anode electrode, and the electrolyte membrane 1 is placed between the force source electrode 12 and the anode electrode. Includes arranged structures. In such MEAs, since the above-described electrolyte membrane of the present invention is used, MEAs having excellent characteristics can be obtained. In FIG. 16, the anode electrode is not shown because it is disposed on the other side of the electrolyte membrane 1.
- the anode electrode and the cathode electrode are not particularly limited, and general electrodes may be used. Further, at least one electrode selected from an anode electrode and a force source electrode may contain an electrolyte obtained by miniaturizing the electrolyte membrane of the present invention.
- a fuel cell 21 shown in FIG. 18 includes the above-described electrolyte membrane 1 of the present invention, a cathode electrode 12, and an anode electrode, and the electrolyte membrane 1 is sandwiched between the anode electrode and the cathode electrode 12.
- the fuel cell includes a fuel supply unit for supplying fuel to the anode electrode, and an oxidant supply unit for supplying oxidant to the cathode electrode.
- the MEA 11 including the anode electrode, the electrolyte membrane 1 and the cathode electrode 12 is formed by a power source cell. 8
- the MEA 11 has a fuel supply manifold 24, an oxidant supply manifold 25, and a refrigerant supply manifold 26. If the fuel cell is air-cooled, a refrigerant supply manifold is not necessarily required. Further, the fuel supply manifold and the oxidant supply manifold need not necessarily be formed in the MEA 11.
- Such a fuel cell uses the above-described electrolyte membrane of the present invention, it has excellent characteristics (for example, excellent power generation characteristics, suppressed fuel crossover, low cost, etc.). It can be a fuel cell.
- the material used for parts other than the electrolyte membrane and the structure thereof are not particularly limited. It may be the same as a general fuel cell (PEFC or direct methanol fuel cell (DMFC)).
- the anode electrode and the force electrode may include Pt as a catalyst and powder of a carbon material as a conductive agent.
- the electrolyte membrane and each of the electrodes may be pressed by, for example, a press.
- the fuel may include at least one gas or liquid selected from hydrogen and hydrocarbons. More specifically, for example, methanol or an aqueous methanol solution may be used. When the fuel is liquid, the fuel may be supplied to the fuel cell from a cartridge or the like.
- Example 1 the structure of the organic molecule was changed by using porous particles as the base material. Four types of samples were prepared.
- Example 1 Each sample in Example 1 was produced as follows.
- Siri force gel (specific surface area: 300 m 2 / cm 3 , average particle size: 2 ⁇ m) was used as a substrate.
- the formation of the organic molecular film on the surface of the base material was performed as follows. First, an alkoxysilane compound containing an epoxy group at the end of the molecular chain (CH 2 (- ⁇ -1) CHCH 2 O (CH 2 ) 1.6 g of a Si (OCH 3 ) 3 ) was dissolved in 40 cc of toluene solvent, and 1 g of silica gel was immersed in this solution and reacted at 70 ° C. for 2 hours.
- the thickness of the organic molecular film was obtained by measuring the pore distribution of the silica gel before the treatment and the silica gel on which the organic molecular film was formed, and comparing the values of the average pore diameter.
- the pore distribution was measured by the nitrogen adsorption method, and the nitrogen gas adsorption isotherm was analyzed by the BJH method to obtain the pore distribution and the average pore diameter.
- the silica gel organic molecular film is formed, after mixing with the 1 0 mass 0/0 of Porite trough Ruo ii ethylene (P TF E) powder and mortar, pressure 5MP a (5 0 Pellet molding at kgf / cm 2 ) yielded an electrolyte membrane (diameter 20 mm, thickness 200 ⁇ ).
- P TF E Porite trough Ruo ii ethylene
- Sampnolet 2-An organic molecular film was formed on the substrate using the same substrate as that of Sample 1 and using an organic molecule different from that of Sample 1.
- the introduction of the organic molecular film onto the surface of the substrate was performed as follows.
- An electrolyte membrane was obtained in the same manner as in Sample 1 using the silica gel formed with an organic molecular film formed as described above.
- An organic molecular film was formed on the substrate using the same substrate as that of Sample 1 and using an organic molecule different from that of Sample 1.
- the introduction of the organic molecular film onto the surface of the substrate was performed as follows.
- the 6 g was dissolved in toluene solvent 4 0 cc, the 1 g of silica gel was immersed in the solution and reacted at room temperature for 2 hours.
- a dehydrochlorination reaction occurs between the hydroxyl group (1 OH) on the surface of the substrate and the mouth group of the chlorosilane compound, and a film comprising organic molecules covalently bonded to the surface of the substrate is formed.
- a dehydrochlorination reaction proceeded as shown in the chemical formula in FIG.
- this organic molecule has a double bond which is a kind of a binding group at the terminal of the main chain, an organic compound can be further laminated.
- Lamination of organic molecules was performed as follows. Was prepared as described above, the silica gel layer was formed consisting of organic molecules, organic molecules laminated (CF 3 CF 2 - C 6 H 4 - (CH 2) 2 B r) 1. 6 g, toluene The solution was immersed in a solution containing 0.4 cc of a solvent and 0.4 g of azoisobutyronitrile (AIBN) as a binding initiator, and reacted at 60 ° C for 2 hours. This The organic molecules covalently bonded to the surface of the substrate by the lamination process are as shown in FIG.
- AIBN azoisobutyronitrile
- An electrolyte membrane was obtained in the same manner as in Sample 1 using the silica gel formed with an organic molecular film formed as described above.
- An organic molecular film was formed on the substrate using the same substrate as that of Sample 1 and using an organic molecule different from that of Sample 1.
- the introduction of the organic molecular film onto the surface of the substrate was performed as follows.
- This alkoxysilane compound is shown in FIG. “Me” including “Me” shown in FIG. 26 means a methyl group (one CH 3 ).
- a dealcoholization reaction occurs between the hydroxyl group (-OH) on the surface of the substrate and the alkoxy group of the alkoxysilane compound, and a film composed of organic molecules covalently bonded to the surface of the substrate 2 (Fig. 27). Is shown in Fig. 2).
- This organic compound has a double bond in the side chain, which is a type of binding group.
- Bonding between adjacent organic molecules was performed as follows. 1 g of the silica gel on which a film composed of organic molecules was formed as described above was immersed in a solution of 40 cc of a toluene solvent containing 0.4 g of AIBN as a binding initiator, and then 60 ° C. The reaction was performed at C for 2 hours. By this reaction, adjacent organic molecules were bonded to each other, and a film as shown in FIG. 28 could be formed on the surface of the substrate 2.
- An electrolyte membrane was obtained in the same manner as in Sample 1 using the silica gel formed with an organic molecular film formed as described above.
- Example 1 Nafion 117 manufactured by DuPont was used as an electrolyte membrane for comparison.
- the size, film thickness, etc. were the same as in Sample 1.
- Samples 1 to 4 had better ionic conductivity than Comparative Example 1. This is presumably because Samples 1 to 4 contain organic molecular membranes that serve as ion conduction pathways, in which functional groups having high-density ion conductivity are arranged in an ordered manner.
- Sample 3 had the highest ionic conductivity. This is because the organic molecular film contained in Sample 3 is a two-layered organic molecular film, and more ion-exchange groups could be introduced.
- Example 2 six types of samples including the same organic molecular film as the above-mentioned sample 1 but having different base materials were prepared.
- Example 2 Each sample in Example 2 was produced as follows. The average pore diameter of the through-holes in the substrate was measured by the same nitrogen adsorption method as in Example 1. The same applies to the following embodiments.
- Porous silica glass (a specific surface area of 200 ni 2 / cm 3 , average through-hole diameter of 4 nm, thickness of 500 / m) was used. The size of the silica glass was 3 cm square. An organic molecular film was formed on the surface of such a substrate using the same method as in Sample 1, and an electrolyte membrane was prepared.
- Samples 5 and 6 were laminated to produce a 1-mm-thick electrolyte. Both samples weighed 50 weight percent of a methoxysilane compound that was a thermopolymerizable organic molecule. /. The contained toluene solution was cast on the surface of one of the samples and dried, and then both samples were stacked and heated to about 80 ° C for bonding. The compound shown in FIG. 30 was used as the methoxysilane compound. The uniaxially penetrating silica glass (thickness: 50 m) used in sample 5 was laminated on the porous silica glass (thickness: 500 / zm) used in sample 6, to obtain a composite silica glass. . Using this composite silica glass as a base material, an organic molecular film was formed in the same manner as in Sample 1 to prepare an electrolyte film.
- a methoxysilane compound that was a thermopolymerizable organic molecule. /.
- a 1 ⁇ m thick polyester film was used as a substrate.
- the finolem was cut into a strip with a width of 5 mm and a length of 100 m using a slitter.
- an organic molecular film was formed on the surface of the belt-shaped substrate by using the same method as in Sample 1.
- 10 sheets of the base material on which the organic molecular film was formed were stacked to form a sheet, and the sheet was wound around the axis using a glass rod having a diameter of 1 mm as an axis (core). When winding, use a precision winding machine to tension the substrate. 8
- the shaft was rotated at a low speed while applying power.
- a very dense electrolyte membrane having a diameter of 11.4 mm was obtained. This was cut by a slitter in a direction perpendicular to the axis, to obtain 10 500 ⁇ m-thick electrolyte membranes. Further, a part of the obtained electrolyte membrane was cut into a 5 mm square (thickness: 500 ⁇ ) so as not to include the axis.
- Sample 10-Silica gel formed with an organic molecular film formed in Sample 1 was mixed with a 10% by weight aqueous solution of polybutyl alcohol in a mortar. This was retained and immobilized in a porous glass having an average pore diameter of 20 ⁇ and a thickness of 500 ⁇ m by suction filtration to obtain an electrolyte membrane.
- the ionic conductivity was improved as compared with Comparative Example 1. Above all, the ionic conductivity of Sample 5 using a substrate having a through-hole only in a direction perpendicular to the film surface was highest. However, a substrate having holes at least in the direction penetrating the electrolyte membrane, such as sample 6, is used. If so, high ionic conductivity could be obtained. In addition, the ionic conductivity of Samples 7 and 8 showed a value between the ionic conductivity of Samples 5 and 6. This indicates that the ionic conductivity can be controlled by combining an arbitrary electrolyte membrane or a composite of an arbitrary substrate as a substrate.
- Example 3 five kinds of samples containing the same organic molecular film as the above-described sample 1 but having a specific surface area per unit volume of the base material used were prepared.
- Example 3 Each sample in Example 3 was produced as follows.
- the porosity ⁇ of the substrate was measured by a nitrogen adsorption method.
- Porous alumina membrane with through-holes as base material (specific surface area 310 m 2 / cm 3 , average through-hole diameter 3 nm, thickness 50; _im, porosity 24 volumes./.) was used.
- An organic molecular film was formed on the surface of such a base material using the same method as in Sample 1, and an electrolyte film was produced.
- porous alumina membrane (specific surface area: 10 Om 2 Z cm 3 , average pore diameter 9 nm, thickness 50 ⁇ , porosity 25% by volume) was.
- An organic molecular film was formed on the surface of such a base material using the same method as in Sample 1, and an electrolyte film was produced.
- a porous alumina membrane having a through hole (specific surface area: 70 m 2 / cm 3 , average through hole diameter: 10 nm, thickness: 50 ⁇ , porosity: 25% by volume) was used as a substrate.
- An organic molecular film was formed on the surface of such a base material using the same method as in Sample 1, and an electrolyte film was produced.
- Sampnole 15-Porous alumina membrane with through-holes as base material (specific surface area 5 O m 2 / cm 3 , average diameter of through-holes 20 nm, thickness 50 ⁇ ⁇ ⁇ , porosity 23 vol% ) was used.
- An organic molecular film was formed on the surface of such a base material using the same method as in Sample 1, and an electrolyte film was produced.
- ionic conductivity was obtained in all of the samples 11 to 15.
- the larger the specific surface area the higher the obtained ionic conductivity.
- the specific surface area is not less than 70 m 2 / c in 3 or the parameter (4 ⁇ ⁇
- Example 3 13 kinds of samples including the same organic molecular film as in Sample 1 described above, except that the porosity ⁇ of the base material used and the average curvature ⁇ of the through holes were changed were prepared.
- the average curvature ⁇ of the substrate was estimated from the air permeability of the substrate.
- Air permeability is defined by the time required for a given volume of gas to pass through a given area of a sample under certain conditions. The air permeability depends on the speed of movement of the gas and the shape of the through-hole.
- the air permeability t (sec) is obtained by calculating the above-mentioned thickness 1 (cm), porosity ⁇ (volume%), average curvature ⁇ and average pore diameter d (nm), and the proportional coefficient C Is represented by the following equation using
- the average curvature ⁇ of the substrate can be determined.
- each parameter in the above equation is used.
- the data was measured as follows.
- the air permeability was measured under the conditions of a permeated gas volume of 10 cm 3 , a sample area of 1 inch 2 , and an applied pressure of 2.3 cmHg, based on ASTM (American Society for Testing and Materials) standards.
- the porosity ⁇ and the average pore diameter d were determined by analysis based on the nitrogen adsorption method and the BJH method, as in the previous examples.
- the proportionality coefficient C was 0.52.
- the calculation method of the average curvature ⁇ is the same in the following embodiments.
- Example 4 Each sample in Example 4 was produced as follows.
- electrolyte membranes were prepared in the same manner. However, the following substrates were used.
- Sample 1 7-Porous silica membrane with through-holes (average pore diameter of through-holes 4 nm, average curvature of through-holes 1.2, porosity 31 1% by volume, thickness 50 m)
- Porous silica membrane with through-holes (average pore diameter of through-holes 4 nm, average curvature of through-holes 1.2, porosity 42% by volume, thickness 50 ⁇ m)
- Sampnore 20-Porous silica membrane with through-holes (average pore diameter 4 nm, Average curvature 1.6, porosity 21 1 volume. / 0 , thickness 50 ⁇ ) —Sample 21 1-Porous silica membrane with through-holes (average pore diameter of through-holes 4 nm, average curvature of through-holes 1.6, porosity 27% by volume, (Thickness 50 ⁇ )
- Sampnore 2 2-Porous silica membrane with through-holes (average pore diameter of through-holes 4 nm, average curvature of through-holes 1.6, porosity 50% by volume, thickness 50 / xm)
- Porous silica membrane with through-holes (average pore diameter of through-holes 4 nm, average curvature of through-holes 1.6, porosity 69% by volume, thickness 50 / zm)
- Example 27-Porous silica membrane with through-holes (average pore diameter 4 nm, average curvature 1.8 through-holes, porosity 63 vol%, thickness 50 / m)
- Sample 2 8-Porous silica membrane with through-holes (average pore diameter of through-holes 4 nm, average curvature of through-holes 1.8, porosity 82% by volume, thickness 50 ⁇ m)
- the ionic conductivity of Sample 16 to Sample 28 prepared in this way and? The alcohol permeability was evaluated. Evaluation of ionic conductivity was performed in the same manner as in Example 1.
- the alcohol permeability of the electrolyte membrane was evaluated using the following method; First, the electrolyte membrane was sandwiched between two glass tubes. At this time, the end surface of the glass tube was brought into contact with the membrane surface of the electrolyte membrane, and when a substance was introduced into the glass tube, the material was brought into contact with the membrane surface of the electrolyte membrane. Next, an aqueous alcohol solution having a concentration of 50 mol% was introduced into one glass tube, and water was introduced into the other glass tube.
- Example 4 the configuration of the organic molecular film was common to all the samples. However, similar results were obtained when the configuration of the organic molecular film was changed. That is, it is considered that the alcohol permeability coefficient of the electrolyte membrane and the parameter ( ⁇ / ⁇ 2 ) have a correlation with each other. Note that the results of Example 4 do not exclude that the alcohol permeability coefficient of the electrolyte membrane and another parameter of the electrolyte membrane are in a correlation with each other. (Example 5)
- Example 5 a sample was prepared in which a substance was arranged so as to fill a gap existing inside the through hole with respect to Sample 19 in Example 4.
- Sample No. 29-Sample 19 is immersed in a toluene solvent containing 10% by weight of methoxysilane compound, a thermopolymerizable organic molecule, as a precursor, and reacted at 80 ° C for 5 hours. With this, the gap existing inside the through-hole was filled.
- FIG. 23 shows the structural formula of the methoxysilane compound as a precursor.
- the obtained electrolyte membrane was substantially nonporous as a result of measuring the specific surface area by the nitrogen adsorption method.
- the term "substantially non-porous" as used herein means that there are no gaps or pores at least exceeding the measurement limit (mean pore diameter: 0.5 nm) that can be measured by the nitrogen adsorption method. are doing.
- Example 4 The results of measuring the alcohol permeability coefficient and ionic conductivity of Sample 29 are shown below.
- the measurement methods of Example 4 and Example 1 were used, respectively.
- Example 6 a fuel cell was manufactured using the electrolyte membrane manufactured in Example 3, and the power generation characteristics were evaluated.
- a fuel cell was fabricated.
- the method for manufacturing the fuel cell is described below.
- MEA was fabricated by arranging the anode and the cathode electrode so as to sandwich the electrolyte membrane on both sides of the electrolyte membrane.
- a fuel cell was manufactured by arranging a carpone separator having a flow path through which fuel and air flow so as to further hold the MEA.
- the anode electrode was prepared by mixing a PtRu catalyst-supported carbon catalyst (Tanaka Kikinzoku Co., Ltd., TEC61E54) with a hydrogen ion conductive polymer electrolyte solution '(Asahi Glass Co., Ltd., Flemion).
- the catalyst paste was applied to a carbon sheet (TG PH060H, manufactured by Toray Industries, Inc.) and dried.
- the force sword electrode was prepared by mixing a carbon catalyst carrying Pt catalyst (Tanaka Kikinzoku Co., Ltd., TEC10E50E) and a hydrogen ion conductive polymer electrolyte solution (Asahi Glass Co., Ltd., Flemion).
- the catalyst paste was applied to a carbon sheet (TGPH060H, manufactured by Toray Industries, Inc.) and dried.
- the area of the power generation region in MEA was set to 4 cm 2 .
- sample 12 as the electrolyte membrane, a fuel cell was fabricated in the same manner as in 30.
- Example 33-Sample 14 was used as the electrolyte membrane. JP2003 / 009368
- Sample 34-A fuel cell was fabricated in the same manner as Sample 30, using Sample 15 as the electrolyte membrane.
- Comparative Example 2-A fuel cell was manufactured in the same manner as in Sample 30, except that Comparative Example 1 was used as the electrolyte membrane.
- the power generation tests of Samples 30 to 34 and Comparative Example 2 thus produced were performed.
- the power generation conditions were as follows: hydrogen gas (supply amount 30 mlZ min, gas temperature 60 ° C, gas relative humidity 70%) as fuel, air as oxidant (supply amount 200 cc / min, gas temperature 60 ° C , The relative humidity of the gas was 70%) and the battery temperature was 60. Endpoints, each sample of the open circuit voltage (OCV), the battery voltage at a current density 0. 1 AZ cm 2 (V) , and to obtain a voltage of the battery at a current density 0. 3 AZ cm 2 (V) . Table 6 shows the results.
- Example 7 a fuel cell was manufactured using the electrolyte membranes and the like manufactured in Examples 4 and 5, and the power generation characteristics thereof were evaluated.
- a fuel cell was fabricated in the same manner as in Sample 30, except that Sample 29 was used as the sample electrolyte.
- a fuel electrode was produced in the same manner as in sample 30. However, an electrode containing silica gel having an organic molecular film formed thereon, which was used when preparing Sample 1, was used as the electrode. The method for manufacturing the electrode is described below.
- a silica gel having an organic molecular film formed thereon and a carbon catalyst (manufactured by Tanaka Kikinzoku Co., Ltd., TEC61E54) supporting PtRu were mixed at a weight ratio of 1: 1 mixed.
- 5% by weight of PTFE was mixed with this mixture in a mortar, and pelletized at a pressure of 5 MPa (50 kgf / cm 2 ) to produce an anode electrode.
- the force sword electrode was fabricated in the same manner as the anode electrode, except that a carbon catalyst supporting Pt on the catalyst (TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.) was used.
- Ponds can be provided.
- the electrolyte membrane of the present invention can be used for various electrochemical devices such as a primary battery, a secondary battery, an electrochemical capacitor, various gas sensors, and an electrochromic element in addition to a fuel cell.
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- Engineering & Computer Science (AREA)
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Description
Claims
Priority Applications (3)
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JP2004530539A JP4637579B2 (ja) | 2002-07-25 | 2003-07-24 | 電解質膜とこれを用いた膜電極接合体および燃料電池 |
EP03792635A EP1548863A1 (en) | 2002-07-25 | 2003-07-24 | Electrolyte membrane, membrane electrode assembly using this and fuel cell |
US10/521,871 US7604887B2 (en) | 2002-07-25 | 2003-07-24 | Electrolyte membrane, membrane electrode assembly using this and fuel cell |
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JP2002217247 | 2002-07-25 | ||
JP2002-217247 | 2002-07-25 |
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PCT/JP2003/009368 WO2004019439A1 (ja) | 2002-07-25 | 2003-07-24 | 電解質膜とこれを用いた膜電極接合体および燃料電池 |
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US (1) | US7604887B2 (ja) |
EP (1) | EP1548863A1 (ja) |
JP (1) | JP4637579B2 (ja) |
CN (1) | CN1672280A (ja) |
WO (1) | WO2004019439A1 (ja) |
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FR2853456A1 (fr) * | 2003-04-04 | 2004-10-08 | Sagem | Micropiles a combustible destinees particulierement aux dispositifs electroniques portables et aux dispositifs de telecommunications |
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JP2006066390A (ja) * | 2004-08-24 | 2006-03-09 | Toyo Technol Inc | 燃料電池のための表面電解質sefc |
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JP2007273387A (ja) * | 2006-03-31 | 2007-10-18 | Noritake Co Ltd | 電極−電解質一体型膜電極接合体およびその製造方法 |
US7534510B2 (en) | 2004-09-03 | 2009-05-19 | The Gillette Company | Fuel compositions |
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JP2010199028A (ja) * | 2009-02-27 | 2010-09-09 | Japan Science & Technology Agency | イオン伝導膜 |
US8211590B2 (en) * | 2005-03-15 | 2012-07-03 | Panasonic Corporation | Proton conducting material, and electrode and fuel cell using the same |
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JP5151063B2 (ja) | 2006-04-19 | 2013-02-27 | トヨタ自動車株式会社 | 燃料電池用電解質膜用多孔質材料、その製造方法、固体高分子型燃料電池用電解質膜、膜−電極接合体(mea)、及び燃料電池 |
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FR2853456A1 (fr) * | 2003-04-04 | 2004-10-08 | Sagem | Micropiles a combustible destinees particulierement aux dispositifs electroniques portables et aux dispositifs de telecommunications |
WO2004091026A2 (fr) * | 2003-04-04 | 2004-10-21 | Sagem Sa | Micropiles a combustible destinees particulierement aux dispositif electroniques portables et aux dispositifs de telecommunications |
WO2004091026A3 (fr) * | 2003-04-04 | 2005-10-27 | Sagem | Micropiles a combustible destinees particulierement aux dispositif electroniques portables et aux dispositifs de telecommunications |
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EP1745523A1 (en) * | 2004-05-04 | 2007-01-24 | Angstrom Power, Inc. | Membranes and electrochemical cells incorporating such membranes |
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US8232025B2 (en) | 2004-05-04 | 2012-07-31 | SOCIéTé BIC | Electrochemical cells having current-carrying structures underlying electrochemical reaction layers |
EP1745523A4 (en) * | 2004-05-04 | 2009-04-01 | Angstrom Power Inc | MEMBRANES AND ELECTROCHEMICAL CELLS WITH SUCH MEMBRANES |
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JP2006066390A (ja) * | 2004-08-24 | 2006-03-09 | Toyo Technol Inc | 燃料電池のための表面電解質sefc |
JP2006100268A (ja) * | 2004-08-30 | 2006-04-13 | Asahi Glass Co Ltd | 固体高分子形燃料電池用膜電極接合体及び固体高分子形燃料電池 |
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US7989117B2 (en) | 2004-09-03 | 2011-08-02 | The Gillette Company | Fuel compositions |
US8211590B2 (en) * | 2005-03-15 | 2012-07-03 | Panasonic Corporation | Proton conducting material, and electrode and fuel cell using the same |
JP2007048551A (ja) * | 2005-08-09 | 2007-02-22 | Toagosei Co Ltd | 直接液体燃料形燃料電池用電解質膜および直接液体燃料形燃料電池 |
JP2007273387A (ja) * | 2006-03-31 | 2007-10-18 | Noritake Co Ltd | 電極−電解質一体型膜電極接合体およびその製造方法 |
US8790842B2 (en) | 2007-09-25 | 2014-07-29 | Societe Bic | Fuel cell systems including space-saving fluid plenum and related methods |
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US9472817B2 (en) | 2008-02-29 | 2016-10-18 | Intelligent Energy Limited | Electrochemical cell and membranes related thereto |
WO2010082406A1 (en) | 2009-01-19 | 2010-07-22 | Toyota Jidosha Kabushiki Kaisha | Electrolyte membrane and method for producing the same |
JP2010199028A (ja) * | 2009-02-27 | 2010-09-09 | Japan Science & Technology Agency | イオン伝導膜 |
JP2016040781A (ja) * | 2011-11-08 | 2016-03-24 | 学校法人早稲田大学 | 電解質膜、膜電極接合体、及び燃料電池 |
JP2016539063A (ja) * | 2013-09-27 | 2016-12-15 | サントル ナスィオナル ド ラ ルシェルシュ スィアンティフィク(セ.エン.エル.エス.) | ハイブリッドアニオン性膜を形成するカチオン性担体 |
JP2019220460A (ja) * | 2018-06-15 | 2019-12-26 | 日本碍子株式会社 | 電気化学セル用電解質、及び電気化学セル |
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JP7293832B2 (ja) | 2018-12-28 | 2023-06-20 | 凸版印刷株式会社 | 電極触媒層、膜電極接合体、および、固体高分子形燃料電池 |
Also Published As
Publication number | Publication date |
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JPWO2004019439A1 (ja) | 2005-12-15 |
JP4637579B2 (ja) | 2011-02-23 |
EP1548863A1 (en) | 2005-06-29 |
US7604887B2 (en) | 2009-10-20 |
US20050260478A1 (en) | 2005-11-24 |
CN1672280A (zh) | 2005-09-21 |
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