WO2005090480A1 - 固体高分子電解質、固体高分子ゲル膜、固体高分子電解質膜、および燃料電池 - Google Patents
固体高分子電解質、固体高分子ゲル膜、固体高分子電解質膜、および燃料電池 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
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- H—ELECTRICITY
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- 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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- 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
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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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
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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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
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
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- 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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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/02—Polyureas
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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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
- Solid polymer electrolyte Solid polymer electrolyte, solid polymer gel membrane, solid polymer electrolyte membrane, and fuel cell
- the present invention relates to an ion-conductive solid polymer electrolyte. More specifically, the present invention relates to a solid polymer gel membrane having high ion conductivity and a solid polymer electrolyte membrane.
- the solid polymer electrolyte membrane includes a fuel cell, an ion conductive membrane for a solid polymer electrolyte fuel cell, a redox battery, an electrodialysis membrane, a reverse osmosis membrane, a nanofiltration membrane, a diffusion dialysis membrane, a gas separation membrane, a pervaporation and Used in the fields of permeation extraction membranes, humidity sensors and gas sensors.
- the solid polymer electrolyte membrane comprising the solid polymer gel membrane of the present invention sandwiched between porous membranes has extremely low methanol permeability, and is used as an electrolyte for direct methanol fuel cells (hereinafter referred to as DMFC). Used as a membrane.
- DMFC direct methanol fuel cells
- PEFC solid polymer electrolyte fuel cell
- methanol can be supplied to the anode side and oxygen or air can be supplied to the power source side to cause an electrochemical reaction, and as a result, electricity is generated I do.
- Solid polymer electrolyte membranes with high proton conductivity have been developed to maintain the characteristics of fuel cells such as high output and high energy density and to realize small and lightweight fuel cells.
- the solid polymer electrolyte membrane used in the DMFC has high ion conductivity while preventing methanol for fuel, i.e., the anode force on the solid polymer electrolyte membrane also reduces the fuel force to the force side. Methanol permeation (crossover) Reduction is required.
- PFS hydrated perfluorocarbon sulfonic acid
- Naphion Membrane registered trademark
- DuPont hydrated perfluorocarbon sulfonic acid
- PFS-based polymers for example, Naphion Membrane (registered trademark) manufactured by DuPont
- hydrated PFS-based polymer membranes have a fundamental limit in methanol-blocking properties because they easily pass (cross-bar) methanol with high affinity for water.
- cross-bar cross-bar
- the crossover of methanol in PFS-based polymer hydrated membranes it is considered to combine different materials based on PFS-based polymer hydrated membranes.
- the above composite has a problem that the high ionic conductivity of the original PFS polymer hydrated membrane is significantly reduced.
- Patent Document 1 discloses that a naphion 112 membrane (trade name, manufactured by DuPont) is used with a meta-type poly-arylene which is impregnated with ar-lin. I have. It has been disclosed that this meta-type polyarline has the same ionic conductivity as Naphion® membrane (registered trademark) and about 1Z3 methanol blocking property of Naphion® membrane (registered trademark). It is still insufficient to use. Further, since expensive Nafion membrane (registered trademark) is further processed, the number of steps is large and complicated, resulting in a more expensive membrane.
- Patent Literature 2 discloses a zwitterionic polymer gel obtained by mixing a graft copolymer comprising a side chain and a polymer gel film formed by forming the zwitterionic polymer gel. .
- This zwitterionic polymer gel is characterized in that the degree of swelling is greatly changed by a change in pH.
- Patent Document 2 has no description regarding the ion conductive membrane. Even when the polymer gel membrane is used as a membrane for a fuel cell, the volume and area of the membrane greatly change due to a change in pH in the fuel cell during power generation. In addition, there is a possibility that the fuel cell itself may be destroyed.
- Patent Document 3 discloses a solid polymer membrane in which a main polymer having an acidic or basic site is impregnated with a subpolymer having a basic or acidic site and a method for producing the same. It has been disclosed. However, this solid polymer membrane still has many problems such as insufficient ionic conductivity.
- Patent document 1 JP 2001-81220A
- Patent document 2 JP-A-64-145464
- Patent Document 3 JP 2001-236973 A
- Patent Document 4 Japanese Patent Publication No. U-503262
- Patent Document 2 K. Tsuruhara, M. Rikukawa, K. Sassemble, N. Ogata, Y. Nagasaki, and M. Kato, Electrochim Acta, 45, 1391 (2000)
- Non-patent Document 3 W. Wieczorek and J.R. Stevens, Polymer, 38, 2057 (1997)
- Non-Patent Document 4 J. Kerrer, A. Ullrich, F. Meier and T. Harig, Solid State
- the present invention has been made to solve the current problems of the PFS-based polymer hydrated membrane, the PFS modified membrane, and various electrolyte membranes as the solid polymer electrolyte for DMFC as described above.
- Another object of the present invention is to provide a low-cost solid polymer electrolyte membrane having high methanol conductivity while maintaining high ionic conductivity.
- the inventors of the present invention have conducted intensive studies on the above problems, and as a result, have found that a composition containing a composition obtained by mixing a polymer solution having a specific acidic group and a polymer solution having a specific basic group is contained.
- solid polymer electrolyte membranes, solid polymer electrolyte membranes, solid polymer gel membranes of specific properties, and solid polymer electrolyte membranes sandwiched between porous polymer membranes are particularly suitable for high-ion conduction.
- the inventors have found that methanol permeability is improved while maintaining the property, and the present invention has been accomplished.
- the present invention is a solid polymer electrolyte containing a composition obtained by mixing a polymer solution having an acidic group and a polymer solution having a basic group,
- the polymer having an acidic group is an aliphatic polymer having at least one selected from the group consisting of a sulfonic acid group, a phosphonic acid group, and a carboxyl group in a side chain, and the polymer having a basic property is an amino group, an amide.
- a solid polymer electrolyte which is an aliphatic polymer or an aromatic polymer having at least one selected from the group consisting of a group and a urea group in a main chain or a side chain.
- the pH value of the composition is 6 or less, or 8 or more, and the functional group equivalent number of the polymer having the acidic group and the polymer having the basic group.
- the ratio of the polymer is 20 / 80-80 / 20, the polymer content is 10-90% by weight, the polymer force having the acidic group is polyperfluorocarbonsulfonic acid, polyacrylamidomethylpropanesulfonic acid.
- the filler is made of siloxane resin, sulfonidani pitch, sulfonidani carbon, montmorillonite, or acidic zeola.
- the amount of the filler is preferably 5 to 300 parts by weight based on the polymer content of 100 parts by weight in the solid polymer electrolyte.
- the total content of the polymer having an acidic group and the polymer having a basic group is 5 to 90% by weight
- the matrix polymer is a polytetrafluroate.
- Polyethylene, polyvinyl chloride, polyvinyl chloride copolymer, styrene acrylonitrile copolymer, vinyl butyl pyrpyridin copolymer, polyethylene, polyethylene butyl alcohol copolymer, polypropylene, polyvinyl chloride vinylidene, or ethylene tetra Preferably, it is a fluoroethylene copolymer and further contains a crosslinking agent, and is crosslinked by heat, light or electron beam.
- the present invention is a solid polymer gel film obtained by forming the solid polymer electrolyte into a film.
- the present invention is a solid polymer electrolyte membrane in which the solid polymer gel membrane is sandwiched between porous membranes.
- the Gurley value of the porous membrane is preferably 100 seconds or less.
- the present invention is a solid polymer electrolyte membrane formed by forming a solid polymer electrolyte containing a matrix polymer.
- the present invention provides the solid polymer electrolyte membrane, the solid polymer gel membrane, or the solid polymer gel membrane in which the solid polymer gel membrane is sandwiched between porous membranes;
- This is a fuel cell including a positive electrode and a negative electrode sandwiching a solid polymer electrolyte membrane.
- a solid polymer electrolyte membrane or a solid polymer electrolyte gel membrane having excellent proton conductivity and methanol blocking properties can be obtained.
- sandwiching a solid polymer gel film having a specific property or the solid polymer gel film containing a filler with a porous film a solid polymer electrolyte membrane having excellent proton conductivity and methanol-blocking properties can be obtained. can get.
- These solid polymer electrolyte membranes are useful as solid polymer electrolyte membranes for fuel cells, especially for DMFCs. Further, the production of the solid polymer electrolyte membrane of the present invention is simple and inexpensive. can do.
- FIG. 1 is a side view showing an example of the solid polymer electrolyte membrane of the present invention.
- FIG. 2 is a side view showing an example of a fuel cell provided with the solid polymer gel membrane of the present invention.
- FIG. 3 is a side view showing an example of a fuel cell including the solid polymer electrolyte membrane of the present invention.
- FIG. 4 is a side view showing another example of the fuel cell including the polymer electrolyte membrane of the present invention.
- the polymer having an acidic group in the present invention may be a polymer having a sulfonic acid group, a phosphonic acid group, or a carboxyl group on the side chain of an aliphatic polymer, and a plurality of these different functional groups may be bonded. May be.
- some or all of the hydrogen atoms bonded to carbon may be replaced with fluorine atoms.
- the polymer having an acidic group does not work even with a random copolymer, a block copolymer, or a cross copolymer copolymerized with copolymerizable vinyl monomers.
- covalent bondable monomer examples include acrylamide, acrylonitrile, butyl acetate, styrene, various (meth) atalylates, vinylpyridine, vinylpyrrolidone, vinylcaprolatatam, and derivatives thereof.
- the monomer is not limited to this, but may be any copolymerizable monomer.
- acrylic acid and “methacrylic acid” are collectively referred to as (meth) acrylic acid
- atalylate and “metharylate” are collectively referred to as (meth) atalylate.
- polymer having an acidic group examples include a PFS resin solution (for example, Naphion resin solution (SE-10072) manufactured by DuPont), polyacrylamidomethylpropanesulfonic acid, and polyacid phosphoshikiethyl metatali.
- PFS resin solution for example, Naphion resin solution (SE-10072) manufactured by DuPont
- polyacrylamidomethylpropanesulfonic acid and polyacid phosphoshikiethyl metatali.
- the sulfonic acid group which is not limited to these, Any material may be used as long as it is formed as an aliphatic polymer having at least one selected from the group consisting of a sulphonic acid group and a carboxyl group
- the polymer having a basic group in the present invention may be a polymer having an amino group, an amide group, or an urea group in the polymer main chain or side chain, and a plurality of these different functional groups may be bonded. May be. In addition, some or all of the hydrogen atoms bonded to carbon may be replaced with fluorine atoms. Furthermore, the polymer having a basic group may be a random copolymer, a block copolymer, or a cross-copolymer copolymerized with copolymerizable bullet monomers.
- polystyrene resin examples include polyacrylamide, polyallylamine (for example, PAA, PAS, etc., manufactured by Nitto Boseki Co., Ltd.), polydimethylaminoethyl (meth) atalylate, aminopolyacrylamide, and polyamino.
- a uniform putty-like or jelly-like composition can be obtained by putting a predetermined amount of these ionic polymers in the form of an aqueous solution or an alcohol solution into a kneader and mixing and stirring. At this time, other additives such as an antioxidant (a radical scavenger or a peroxide decomposer for a hydrid) and a colorant may be mixed together. By forming this composition into a film, the solid polymer gel film of the present invention is obtained.
- an antioxidant a radical scavenger or a peroxide decomposer for a hydrid
- the above-mentioned polymer having an acidic group and the polymer having a basic group may be mixed in plural types. Further, copolymerization of a monomer having an acidic group and a monomer having a basic group It is also possible to use a copolymer of a non-polar monomer and a monomer having an acidic group, or a copolymer of a non-polar monomer and a monomer having a basic group.
- the non-polar monomer include styrene derivatives, methacrylates, acrylonitrile, butyl acetate, other monomers having a butyl group, and monomers having an aromatic ring.
- the pH value of the composition obtained by mixing the polymer solution having an acidic group and the polymer solution having a basic group is in the range of 0 or more and 6 or less, or 8 or more and 14 or less, it is desirable. Can exhibit ionic conductivity and methanol-blocking properties.
- P H value is 0 or more and 6 or less of the composition is obtained by mixing the polymer solution with a polymer solution and a weak basic group having a strongly acidic group.
- a predetermined amount of a PFS resin solution for example, Naphion resin solution (SE-10072) manufactured by DuPont
- a polyacrylamidomethylpropanesulfonic acid solution is mixed with a polyacrylamide solution, polybulpyrrolidone, or polybulpyridine.
- a composition having a pH value of not less than 6 and not more than 6 can be obtained, but the composition is not limited thereto.
- a composition having a pH value of 8 or more and 14 or less can be obtained by mixing a polymer solution having a weakly acidic group and a polymer solution having a strongly basic group.
- the pH value is 8 or more and 14 or less.
- the power to obtain the composition is not limited to these.
- the ratio of the equivalent number of these functional groups (the equivalent number of the acidic group in the polymer having the acidic group, Z basic group) Is preferably 20Z80-80Z20, more preferably 30-70-70-30, particularly preferably 40-60-60-40.
- the ratio of functional group equivalent numbers is within the range of 20-80-80-20, sufficient ionic conductivity can be obtained.
- the number of functional group equivalents is determined by neutralization titration.
- a method of adsorbing a polymer having a basic group on the surface of a commercially available Nafion membrane is also conceivable.
- the Nafion membrane registered trademark
- the Nafion membrane is immersed in an aqueous solution of a polyacrylamide-based polymer.
- the desired ionic conductivity and meta It was a power that did not provide the ability to block the knoll.
- effective ionic conductivity cannot be obtained simply by impregnating a polymer having a basic group into a membrane having a sulfonic acid group.
- the polymer content in the composition obtained by mixing is preferably 10 to 90% by weight, more preferably. Is from 12 to 80% by weight, particularly preferably from 15 to 70% by weight.
- the polymer content in the composition obtained by mixing is 10% by weight or more, sufficient ionic conductivity is obtained.
- the polymer content in the composition obtained by mixing is 90% by weight or less, the gelled resin composition itself does not become brittle and forms a membrane having mechanical strength as an electrolyte membrane. It comes out.
- a filler may be added to a composition obtained by mixing the above-mentioned polymer solution having an acidic group and the polymer solution having a basic group.
- the filler to be added include siloxane resin, sulfonated pitch, sulfonated carbon, montmorillonite, and acidic zeolite.
- the raw material pitch for sulfonation include coal pitch, petroleum pitch, and synthetic pitch.A synthetic pitch excellent in chemical purity and quality stability (for example, AR pitch manufactured by Mitsubishi Gas Chemical Company, Inc.) ) Is preferred.
- the raw material carbon for sulfonation include fullerene, carbon nanotube, carbon nanohorn, and carbon nanofiber.
- the amount of the filler added to the filler is preferably 5-300 parts by weight, more preferably 10-200 parts by weight, based on 100 parts by weight of the ionic polymer.
- the amount of the filler is 5 parts by weight or more, the effect of adding the filler, that is, uniformity of the kneaded state between the ionic polymers and improvement in the strength of the kneaded jelly composition can be obtained.
- the added amount of the filler is 300 parts by weight or less, the gel resin composition itself does not become brittle, and a membrane having mechanical strength as an electrolyte membrane can be formed.
- the solid polymer electrolyte membrane of the present invention is obtained by sandwiching both sides of the solid polymer electrolyte gel membrane 1 with a porous membrane 2.
- the Gurley value (indicating the air permeability of the membrane) of the porous membrane 2 used in the present invention is preferably 100 seconds or less, more preferably 80 seconds or less, particularly preferably 50 seconds or less.
- the Gurley value, the paper or paperboard surface area 642 mm 2 refers to the time that air 100ml passes.
- the Gurley value is measured by the Gurley tester method described in JIS P8117.
- the membrane substrate examples include polyolefin films such as polyethylene and polypropylene, fluorine films represented by polytetrafluoroethylene (PTFE), polyimides, and engineering plastics such as polyphenylene ether.
- PTFE polytetrafluoroethylene
- the force that can be achieved is not particularly limited as long as it satisfies the above physical properties.
- the matrix polymer in the present invention is kneaded with the polymer having an acidic group and the polymer having a basic group, thereby forming a film as a solid polymer electrolyte membrane of the composition, mechanical strength, and resistance to resistance.
- the properties such as chemical properties are improved.
- the matrix polymer examples include polyethylene, polypropylene, polychlorinated vinyl, polychlorinated bilidene, polychlorinated vinyl copolymer, polyparabutylenol, polystyrene, and styrene-acrylonitrile copolymer. , Butyl acetate-butyl pyridine copolymer, polyvinyl alcohol, polyethylene-butyl alcohol copolymer, polyimide, polyvinylidene imidazole, polyoxazole, polycarbonate, polyethylene oxide, polyphenylene oxide, polytetrafluoroethylene, And ethylene tetrafluoroethylene copolymer.
- the matrix polymer is not particularly limited as long as it satisfies the physical properties described above, which may contain a plurality of these.
- Predetermined amounts of the polymer having an acidic group, the polymer having a basic group, and the matrix polymer are placed in a kneader, and the mixture is stirred to obtain a uniform composition.
- a filler and other additives such as a cross-linking agent, an antioxidant (radical scavenger, a peroxide decomposer for a hide) or a coloring agent may be mixed together.
- the polymer having an acidic group and the polymer having a basic group are usually added in the form of a powder, an aqueous solution, an alcohol solution, or an organic solution. Further, other organic solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide and the like can be added and kneaded.
- a polymer having an acidic group, a polymer having a basic group, and a matrix polymer At the time of mixing, the total content of the polymer having an acidic group and the polymer having a basic group in the composition obtained by mixing is preferably 5 to 90% by weight, more preferably 8 to 80% by weight. %, Particularly preferably 10-70% by weight.
- the total content of the polymer having an acidic group and the polymer having a basic group in the composition is 5% by weight or more, sufficient ionic conductivity is obtained.
- the total content of the polymer having an acidic group and the polymer having a basic group in the composition is 90% by weight or less, the composition itself does not become brittle and a free-standing film can be formed.
- the crosslinking agent reacts with a polymer having an acidic group, a polymer having a basic group, and Z or a matrix polymer to form a crosslinked structure.
- a polymer having an acidic group or the polymer having a basic group reacts with a polymer having an acidic group, a polymer having a basic group, and Z or a matrix polymer to form a crosslinked structure.
- the cross-linking agent to be added include peroxides, diepoxy compounds, diisocyanate conjugates, and dianhydrides, and peroxides are preferably used.
- peroxidic stilt for example, a peracid stilt described in a catalog of NOF CORPORATION can be used. Specific examples include t-butylperoxylaurate, t-butylperoxysopropinolemonocarbonate, t-butynoleoxybenzoate, di-t-butynoleveroxide and the like.
- the amount of the peroxide to be added is 0.1 to 10% by weight based on the total amount of the polymer (the total amount of the polymer having an acidic group, the polymer having a basic group, and the matrix polymer). , Preferably 0.2-5% by weight, more preferably 0.2-1% by weight. It is effective that the temperature for performing the cross-linking reaction is about 80 ° C to 130 ° C, and the cross-linking time is suitably about 1 to 160 minutes. It may be appropriately selected depending on the type of the polymer, the matrix polymer, and the crosslinking agent to be added.
- a photoinitiator may be used to crosslink with ultraviolet rays or an electron beam (for example, gamma rays). May be performed. These means may be used in combination to introduce a crosslinking reaction and a crosslinking structure.
- the solid polymer electrolyte membrane of the present invention comprises a polymer having an acidic group and a polymer having a basic group. It is obtained by forming a film of a limer and a matrix polymer. An example of a specific film forming method is shown below. First, a predetermined amount of an aqueous solution of naphthion resin (registered trademark) as a polymer having an acidic group, an aqueous solution of polyacrylamide as a polymer having a basic group, and polytetrafluoroethylene as a matrix resin are placed in a mortar, and uniformly mixed. Mix and knead until complete.
- naphthion resin registered trademark
- the putty-like material is sandwiched between SUS plates and pressed to a predetermined thickness.
- the film thickness may be such that the desired ionic conductivity and methanol rejection are achieved and the film is formed as a self-supporting film.
- it is 10 m or more and 500 m or less, preferably 20 m or more and 300 ⁇ m or less, more preferably 30 ⁇ m or more and 200 ⁇ m or less.
- the solid polymer electrolyte membrane, the solid polymer gel membrane 1 produced as described above, and the solid polymer electrolyte formed by sandwiching the solid polymer gel membrane 1 with the porous membrane 2 The methanol permeation rate of the membrane is 2 mgZcm 2 Zmin or less, preferably 1.8 mg / cm / min or less, more preferably 1.6 mgZcm 2 Zmin or less.
- the solid polymer gel membrane 1 of the present invention As shown in FIGS. 2 to 4, the solid polymer gel membrane 1 of the present invention, a solid polymer electrolyte membrane in which the solid polymer gel membrane 1 is sandwiched between porous membranes 2, or a matrix polymer is included.
- a fuel cell having excellent methanol blocking property while maintaining high ion conductivity can be obtained.
- a gas diffusion layer 4 may be provided on the surfaces of the positive electrode 3a and the negative electrode 3b. Gases such as methanol and oxygen used for power generation are diffused and uniformly distributed on the surfaces of the positive electrode 3a and the negative electrode 3b by the gas diffusion layer 4.
- the ionic conductivity was measured according to the following method.
- the solid polymer electrolyte of the present invention, the solid polymer electrolyte membrane 5, the solid polymer gel membrane 1, and the solid polymer gel membrane 1 were converted to a porous polyolefin using an impedance analyzer SI1260 manufactured by Solartron, UK.
- the high-frequency impedance of the solid polymer electrolyte membrane sandwiched between the membranes was measured at 25 ° C.
- the DC component R was read from the Cole-Cole plot, and the proton conductivity (that is, ionic conductivity) was calculated.
- the Cole-Cole plot is an arc graph of a real part versus an imaginary part of a complex ratio to show the orientation polarization of a substance.
- the ionic conductivity of Nafion 112 and Nafion 117 (trade name, manufactured by DuPont) sufficiently immersed in distilled water was 2.2 SZm and 2.5 SZm, respectively.
- Methanol permeability was measured according to the following method.
- An aqueous solution having an ionic polymer concentration of 0.2% was prepared, and the pH of the aqueous solution was measured at 25 ° C.
- the putty-like material was charged in a spacer having a thickness of 0.5 mm, and both surfaces of the obtained solid polymer gel film 1 were sandwiched between platinum electrodes to measure ionic conductivity. As a result, it was 2.2 SZm.
- Example 1 The putty-like product obtained in Example 1 was charged in a 0.5 mm spacer, and both surfaces were covered with a porous polyolefin membrane (manufactured by Teijin DSM Soltec, Sorpore 7P07B, Gurley value: 4 seconds, ZlOOml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 1. OS / m.
- the methanol permeation rate in a 30% aqueous methanol solution was 0.7 mg / cm 2 Z min.
- the aqueous solution of Nafion (registered trademark) of Example 1 was concentrated using an evaporator to obtain a 21% aqueous solution. 9.4 parts of this concentrated Nafion (registered trademark) aqueous solution and 10 parts of a polyacrylamide-based copolymer aqueous solution (Arakawa Chemical Industries, Ltd., KW-387-20, 20% aqueous solution) (polymer concentration in the composition: 21 %, Ratio of acid-base equivalent number: 60Z40) Kneaded in a mortar. When kneaded, a white putty-like material was obtained which was slightly harder than that obtained in Example 1. The pH value of a 0.2% aqueous solution of this putty was 3.50. This putty-like material was formed into a film in the same manner as in Example 1. The ionic conductivity of the obtained solid polymer gel membrane 1 having a thickness of 0.5 mm was 3.3 SZm.
- Example 3 The putty-like product obtained in Example 3 was charged in a 0.5 mm spacer, and both surfaces were covered with a porous polyolefin membrane (manufactured by Teijin DSM Soltec, Sorpore 7P07B, Gurley value: 4 seconds ZlOOml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 2.2 SZ m.
- the methanol permeation rate in a 30% aqueous methanol solution was 0.3 mg / cm 2 Z min.
- this putty-like material was charged in a spacer having a thickness of 0.5 mm, and both surfaces of the obtained solid polymer gel membrane 1 were sandwiched between platinum electrodes, and ionic conductivity was measured. As a result, it was 0.51 SZm.
- Example 1 The putty-like product obtained in Example 1 was charged in a 0.5 mm spacer and both surfaces were covered with a porous polyolefin membrane (Espoir N37, manufactured by Mitsui Chemicals, Inc., Gurley value: 900 seconds, ZOOOOml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 0.008 SZm.
- the methanol permeation rate with a 30% aqueous methanol solution should be 0.1 mgZcm 2 Zmin or less.
- this putty-like material was charged in a 0.5 mm-thick spacer, and both surfaces were covered with a porous polyolefin membrane (manufactured by Teijin DSM Soltec, Solpore 7P07B, Gurley value: 4 seconds / 100 ml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 1.2 SZm.
- the methanol permeation rate with a 30% aqueous methanol solution was 0.82 mgZcm 2 Zmin.
- this putty-like material was placed in a spacer having a thickness of 0.5 mm, and both surfaces of the obtained solid polymer gel membrane 1 were sandwiched between platinum electrodes, and ionic conductivity was measured. The result was 0.05 SZm.
- this jelly-like material was charged in a 0.2 mm-thick spacer, and both surfaces were covered with a porous polyolefin membrane (Solpore 7P07B, manufactured by Teijin DS Soltech, Gurley value: 4 seconds, ZlOOml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 0.22 S / m.
- the methanol permeation rate in a 30% aqueous methanol solution is 1.68 mg, cm Z min.
- the jelly-like material was charged in a spacer having a thickness of 0.5 mm, and both surfaces of the obtained solid polymer gel membrane 1 were sandwiched between platinum electrodes, and the ionic conductivity was measured. As a result, it was 1.2 SZm.
- Example 14 The jelly obtained in Example 14 was charged into a 0.5 mm spacer and both surfaces were covered with a porous polyolefin membrane (Solpore 7P07B, Teijin DS Soltech, Gurley value 4 seconds, 100 ml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 1.OS Zm, and the methanol permeation rate in a 30% aqueous methanol solution was 0.8 mgZcm 2 Zmin.o
- the polyallylamine aqueous solution of Example 14 was concentrated with an evaporator to obtain a 28% solution. 5 parts of this concentrated polyallylamine aqueous solution and 5 parts of an acrylic acid polymer aqueous solution (Arakawa Chemical Industries, Polymer Set HP-710, 30% aqueous solution) (polymer concentration in the composition: 29%, acid Z base equivalent) Number ratio: 54Z46) Kneaded in a mortar. When kneaded, a transparent jelly-like material slightly harder than that obtained in Example 1 was obtained. The pH value of a 0.2% aqueous solution of the jelly was 10.3. This jelly-like material was formed into a film in the same manner as in Example 1. The ionic conductivity of the obtained solid polymer gel membrane 1 having a thickness of 0.5 mm was 4.8 SZm.
- Example 17 The jelly-like material obtained in Example 17 was charged into a 0.5 mm spacer, and both sides were porous.
- Polyolefin membrane manufactured by Teijin DSoltech, Solpore 7P07B, Gurley value 4 seconds, ZlOOml.
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 2.2 S Zm, and the methanol permeation rate in a 30% aqueous methanol solution was 0.5 mgZcm 2 Zmin.o
- Example 17 The jelly obtained in Example 17 was charged into a 0.5 mm spacer and both surfaces were covered with a porous polyolefin film (Espoor N37, manufactured by Mitsui Chemicals, Inc., Gurley value 900 seconds, ZOOOOml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 0.002 SZm, and the methanol permeation rate in a 30% aqueous methanol solution was 0.3 mgZcm 2 Zmin or less.
- Example 20 The jelly-like material obtained in Example 20 was charged into a 0.5 mm spacer, and both surfaces were covered with a porous polyolefin membrane (manufactured by Teijin DSM Soltec, Sorpore 7P07B, Gurley value 4 seconds, ZlOOml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 3.6 S Zm, and the methanol permeation rate with a 30% aqueous methanol solution was 0.96 mg Zcm 2 Zmin.
- this jelly-like material was charged in a spacer having a thickness of 1. Omm, the both surfaces of the obtained solid high molecular gel film 1 were sandwiched between platinum electrodes, and the ionic conductivity was measured. The result was 4.6 SZ m.
- Example 22 The jelly-like material obtained in Example 22 was charged into a 1. Omm spacer, and both surfaces were covered with a porous polyolefin membrane (Solpore 7P07B, Teijin DS Soltech, Gurley value 4 seconds, ZlOOml).
- the ionic conductivity of the obtained solid polymer electrolyte membrane was 2.3 S Zm, and the methanol permeation rate in a 30% aqueous methanol solution was 1.3 mgZcm 2 Zmin.o
- a Nafion membrane (Nafion 112, thickness 50 m) was immersed in a polyacrylamide copolymer aqueous solution (Arakawa Chemical Industries, KW-387-20, 20% aqueous solution) at 60 ° C for 100 hours, and then lightly washed with water. Its ionic conductivity was 0.0009 SZm. Further, the methanol permeation rate was 3.1 mgZcm 2 Zmin. Thus, simply impregnating a polymer having a basic group into a membrane having a sulfonic acid group did not provide an effective methanol-blocking property.
- Acrylic acid polymer aqueous solution (Arakawa Chemical Industries, HP-710, 30% aqueous solution) Acrylamide-based polymer solution (Arakawa Chemical Industries, KW-387-20, 30% aqueous solution) in a mortar with 3 parts (polymer concentration in composition: 30%, acid Z base equivalent ratio: 50Z50) Kneaded.
- a colorless jelly-like substance was obtained, and the pH value of a 0.2% aqueous solution of the jelly-like substance was 6.9.
- this jelly-like material was charged into a spacer having a thickness of 0.2 mm, and the ionic conductivity of the obtained solid polymer gel membrane 1 was measured. As a result, it was 0.002 S / m.
- composition Polymer concentration: 6%, ratio of acid Z base equivalent number: 50Z50 Kneaded in a mortar. When kneading, almost no precipitate was formed.
- the pH value of a 0.2% aqueous solution of this composition was 7.21.
- This putty-like composition was sandwiched between SUS plates and pressed to obtain a solid polymer electrolyte membrane 5 having a thickness of 100 / zm. This was placed in a hot air drying oven at 80 ° C and dried. Both surfaces of the solid polymer electrolyte membrane 5 were sandwiched between platinum electrodes, and the ionic conductivity was measured. as a result, 5 ⁇ 10— / m. The methanol permeation rate was 1 mg / cm 2 / min.
- Example 2 The same procedure as in Example 1 was carried out except that PTFE was not added. 20 parts of Nafion aqueous solution (Dupont, SE-10072, 11% aqueous solution) and 20 parts of polyacrylamide copolymer aqueous solution (Arakawa Chemical Industries, KW-387-20, 20% aqueous solution) 20 parts (acid-base equivalent number ratio) : 60/40) was kneaded in a mortar to give a white putty-like composition. This putty-like composition was sandwiched between SUS plates and pressed to obtain a solid polymer electrolyte membrane having a thickness of 100 m. This was placed in a hot-air drying oven at 80 ° C and dried, but it did not become a free-standing film and was brittle.
- Nafion aqueous solution Duont, SE-10072, 11% aqueous solution
- polyacrylamide copolymer aqueous solution Arakawa Chemical Industries, KW-387-20, 20%
- Polyacrylic acid aqueous solution (Arakawa Chemical Industries, Polymer Set HP-710, 30% aqueous solution) 3 parts (ratio of acid Z base equivalent: 64Z36) and polyallylamine aqueous solution (Nitto Boseki, PA A-10C) 4 parts), 1.5 parts of PTFE (ionic polymer concentration in the composition: 46%), and 6 parts of siloxane resin (X-12, 20% solution, manufactured by Shin-Etsu-Dagakusha).
- PTFE ionic polymer concentration in the composition: 46%)
- siloxane resin X-12, 20% solution, manufactured by Shin-Etsu-Dagakusha
- Example 28 The aqueous naphion solution of Example 1 was concentrated by an evaporator to obtain a 21% solution. 9.4 parts of the concentrated aqueous naphion solution, 10 parts of a polyacrylamide copolymer aqueous solution (Arakawa Chemical Industries, KW-387-20, 20% aqueous solution) (ratio of the number of acid-base equivalents: 60,40), and PTFE7 Part (ionic polymer concentration in the composition: 36%) and 3 parts of acid zeolite were kneaded in a mortar. When kneaded, a white putty-like composition slightly harder than that obtained in Example 1 was obtained.
- a polyacrylamide copolymer aqueous solution Arakawa Chemical Industries, KW-387-20, 20% aqueous solution
- PTFE7 Part ionic polymer concentration in the composition: 36%
- the putty-like composition was sandwiched between SUS plates and pressed to obtain a solid polymer electrolyte membrane 5 having a thickness of 100 m. This was placed in a hot air drying oven at 80 ° C and dried. Both surfaces of the solid polymer electrolyte membrane 5 were sandwiched between platinum electrodes, and the ionic conductivity was measured. The ionic conductivity was 3.3 SZm. The methanol permeation rate was 0.9 mgZcm 2 Zmin.
- Example 1 5 parts of Nafion aqueous solution (manufactured by DuPont, SE-10072, 5.5% aqueous solution) and 5 parts of polyacrylamide copolymer aqueous solution (manufactured by Arakawa Chemical Industries, KW-387-20, 10% aqueous solution) 5 parts (acid-base equivalent Number ratio: 60Z40), 10 parts of PTFE (ionic polymer concentration in the composition: 7.2%), and 3 parts of acid zeolite were kneaded in a mortar. When kneaded, it became a white soft rice cake. Next, the same operation as in Example 1 was performed to obtain a solid polymer electrolyte membrane 5, and the ionic conductivity was measured. A result, was a 1. 5 X 10- 3 SZm. The methanol permeation rate was 0.7 mgZ cm / min.
- Polyacid phosphoshethyl ethyl methacrylate (trade name: Phosmer M homopolymer, 11% IPA solution, manufactured by New Chemical Company) 7.6 parts and 0.57 parts of 50% polyacrylamide aqueous solution (acid-base equivalent number ratio) : 50Z50), 2.0 parts of polyvinyl chloride powder (ionic polymer concentration in the composition: 36%), and 3 parts of siloxane resin (X-12, 20% solution manufactured by Shin-Etsu Danigaku Co., Ltd.) And 2 parts of dimethylformamide were kneaded in a mortar. When kneaded, it became a colorless and soft! / Putty. The subsequent operation was in accordance with Example 1. The ionic conductivity of the obtained solid polymer electrolyte membrane 5 was measured, and as a result, was 8 ⁇ 10— ⁇ Zm. The methanol permeation rate is 0.5 mg / cm / min.
- Example 8 was carried out in the same manner as in Example 8 except that a polybutyl alcohol powder was used instead of the polychlorinated butyl powder. When kneaded at 80 ° C, it became a black soft jelly-like material. The subsequent operation was in accordance with Example 1. As a result of measuring the ionic conductivity of the obtained solid polymer electrolyte membrane 5, it was 4. OSZm. The methanol permeation rate was 1.8 mg / cmV mill.
- Example 8 The composition in Example 8, that is, polyacid phosphoshikiethyl methacrylate (trade name: Phosmer M homopolymer, 11% IPA solution, manufactured by New Chemical Company) 7.6 parts, 50% aqueous solution of polyatalylamide 0. 57 parts (ratio of the number of acid-base equivalents: 50750), 2.0 parts of polychloride butyl powder (concentration of ionic polymer in resin composition: 36%), siloxane resin (manufactured by Shin-Etsu Rigaku Co., Ltd. X—12, 20% solution) To 3 parts of dimethylformamide and 2 parts of dimethylformamide, 1% by weight of t-butylbenzoxybenzoate was added as a crosslinking agent.
- Phosmer M homopolymer 11% IPA solution, manufactured by New Chemical Company
- the obtained jelly-like composition was sandwiched between SUS plates and pressed to obtain a solid polymer electrolyte membrane 5 having a thickness of 100 m. Heat this to 80 ° C It was placed in an air drying oven and dried. Further, a cross-linking reaction was carried out at 120 ° C. in a heat press machine, whereby a film-shaped solid polymer electrolyte membrane 5 was obtained. Both surfaces of this film were sandwiched between platinum electrodes, and the ionic conductivity was measured. As a result, it was 2 X 10— ⁇ Zm. The methanol transmission rate was 0.9 mgZcm 2 Zmin.
- Tables 1 and 4 summarize the results of the examples and comparative examples.
- Example 7 10 parts mer (201 ⁇ 2 aqueous solution) 10 parts * * * * * * 900 0.008
- Example 9 10 parts mer (20% aqueous solution) 10 parts (20% solution) 4 parts 3.6 16 60/40 * 4 1.2 0.82 naphion (5.5% water soluble polyacrylamide-based copoly
- Example 13 Polyacrylic acid-based copoly polyallylamine (10% aqueous solution
- Solid polymer electrolyte membranes include fuel cells, ion conductive membranes for solid polymer electrolyte fuel cells, redox batteries, electrodialysis membranes, reverse osmosis membranes, nanofiltration membranes, diffusion dialysis membranes, gas separation membranes, and osmosis membranes. It is used in the fields of vaporization and permeation extraction membranes, humidity sensors, gas sensors, and has extremely low methanol permeability, and is industrially useful because it is used as an electrolyte membrane for DMFC.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007273203A (ja) * | 2006-03-31 | 2007-10-18 | National Institute Of Advanced Industrial & Technology | 架橋型高分子電解質膜 |
WO2010151227A1 (en) * | 2009-06-26 | 2010-12-29 | Nanyang Technological University | Energy charge storage device using a printable polyelectrolyte as electrolyte material |
WO2011044778A1 (zh) * | 2009-10-16 | 2011-04-21 | 中国科学院大连化学物理研究所 | 芳香族聚合物离子交换膜及其复合膜在酸性电解液液流储能电池中的应用 |
CN105794031A (zh) * | 2013-11-29 | 2016-07-20 | 旭化成株式会社 | 高分子电解质膜 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003501516A (ja) * | 1999-04-30 | 2003-01-14 | へーリング トーマス | 複合体および複合膜 |
JP2003535940A (ja) * | 2000-06-02 | 2003-12-02 | エスアールアイ インターナショナル | 高分子組成物 |
JP2004502008A (ja) * | 2000-05-19 | 2004-01-22 | ウニヴェルズィテート ステュットガルト | スルフィナートアルキル化を介した共有結合架橋ポリマーおよびポリマー膜 |
JP2004335231A (ja) * | 2003-05-06 | 2004-11-25 | Nagaoka Univ Of Technology | 固体高分子電解質その製造方法及びそれを用いた固体高分子形燃料電池 |
-
2005
- 2005-03-02 WO PCT/JP2005/003484 patent/WO2005090480A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003501516A (ja) * | 1999-04-30 | 2003-01-14 | へーリング トーマス | 複合体および複合膜 |
JP2004502008A (ja) * | 2000-05-19 | 2004-01-22 | ウニヴェルズィテート ステュットガルト | スルフィナートアルキル化を介した共有結合架橋ポリマーおよびポリマー膜 |
JP2003535940A (ja) * | 2000-06-02 | 2003-12-02 | エスアールアイ インターナショナル | 高分子組成物 |
JP2004335231A (ja) * | 2003-05-06 | 2004-11-25 | Nagaoka Univ Of Technology | 固体高分子電解質その製造方法及びそれを用いた固体高分子形燃料電池 |
Non-Patent Citations (1)
Title |
---|
KAMATA M. ET AL: "San Enkisei Polymer o Mochiita Proton Dendosei Maku no Sakusei to Hyoka (Preparation and evaluation of a proton conductivity film comparing acid and basic polymer)", THE ELECTROCHEMICAL SOCIETY OF JAPAN SORITSU 70 SHUNEN KINEN TAIKAI KOEN YOKOSHU, 25 March 2003 (2003-03-25), pages 318, XP002998231 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007273203A (ja) * | 2006-03-31 | 2007-10-18 | National Institute Of Advanced Industrial & Technology | 架橋型高分子電解質膜 |
WO2010151227A1 (en) * | 2009-06-26 | 2010-12-29 | Nanyang Technological University | Energy charge storage device using a printable polyelectrolyte as electrolyte material |
US9754727B2 (en) | 2009-06-26 | 2017-09-05 | Nanyang Technological University | Energy charge storage device using a printable polyelectrolyte as electrolyte material |
WO2011044778A1 (zh) * | 2009-10-16 | 2011-04-21 | 中国科学院大连化学物理研究所 | 芳香族聚合物离子交换膜及其复合膜在酸性电解液液流储能电池中的应用 |
US9276282B2 (en) | 2009-10-16 | 2016-03-01 | Dalian Rongke Power Co., Ltd. | Aromatic polymer ion exchange membranes, its composite membrane, and its application in acidic electrolyte flow battery |
CN105794031A (zh) * | 2013-11-29 | 2016-07-20 | 旭化成株式会社 | 高分子电解质膜 |
EP3076465A1 (en) * | 2013-11-29 | 2016-10-05 | Asahi Kasei Kabushiki Kaisha | Polymer electrolyte membrane |
EP3076465A4 (en) * | 2013-11-29 | 2017-05-10 | Asahi Kasei Kabushiki Kaisha | Polymer electrolyte membrane |
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