WO2008004567A1 - Membrane et pile à combustible à électrolyte polymère solide - Google Patents

Membrane et pile à combustible à électrolyte polymère solide Download PDF

Info

Publication number
WO2008004567A1
WO2008004567A1 PCT/JP2007/063343 JP2007063343W WO2008004567A1 WO 2008004567 A1 WO2008004567 A1 WO 2008004567A1 JP 2007063343 W JP2007063343 W JP 2007063343W WO 2008004567 A1 WO2008004567 A1 WO 2008004567A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer electrolyte
electrolyte membrane
solid polymer
monomer
vinyl monomer
Prior art date
Application number
PCT/JP2007/063343
Other languages
English (en)
Japanese (ja)
Inventor
Masahiro Kurokawa
Yoshihiro Gocho
Original Assignee
Mitsubishi Gas Chemical Company, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Company, Inc. filed Critical Mitsubishi Gas Chemical Company, Inc.
Priority to JP2008523700A priority Critical patent/JPWO2008004567A1/ja
Publication of WO2008004567A1 publication Critical patent/WO2008004567A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04197—Preventing means for fuel crossover
    • 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]
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • 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
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2335/06—Copolymers with vinyl aromatic monomers
    • 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]
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid polymer electrolyte membrane and a fuel cell excellent in proton conductivity and methanol permeation blocking properties.
  • PEFC polymer electrolyte fuel cell
  • DMFC direct methanol fuel cell
  • an electrochemical reaction occurs by supplying methanol to the negative electrode side and oxygen or air to the positive electrode side. Is generated.
  • a hydrated perfluorocarbon sulfonic acid (hereinafter referred to as PFS) polymer for example, Nafion [registered trademark]
  • PFS hydrated perfluorocarbon sulfonic acid
  • a hydrated PFS polymer membrane has a high affinity with water, and has a theoretical limit to methanol permeation prevention properties as soon as it permeates methanol.
  • As a means of reducing the methanol crossover of PFS polymer hydrated membranes it is conceivable to combine different materials based on PFS polymer hydrated membranes. However, such a composite significantly reduced the high ionic conductivity of the original PFS polymer hydrated membrane.
  • a naphthyl (registered trademark) membrane is impregnated with arlin to form polyaline, thereby exhibiting the same ionic conductivity as the naphth ion (registered trademark) membrane.
  • the permeation amount of methanol per unit time can be suppressed to about 1 Z3 as compared with a naphthion (registered trademark) membrane (for example, see Patent Document 1).
  • the use of the above membrane as an electrolyte membrane for DMFC is still inadequate in terms of methanol permeation blocking properties.
  • the expensive naphthion (registered trademark) film is further processed, the number of steps becomes complicated and the film becomes more expensive.
  • an acidic monomer is graft-polymerized on a porous membrane (for example, see Patent Document 2), and a matrix monomer, an ion exchange monomer and an alignment monomer are copolymerized (for example, a patent).
  • Reference 3 those in which an acidic or basic monomer is graft-polymerized on a porous membrane and an inorganic filler is further added (for example, see Patent Document 4), those in which a porous membrane is filled with a cation exchange resin (for example, Patent Document 5), and polymers obtained by doping acid with a polymer of acroaminotetrazole or butyrazole (for example, see Patent Document 6) are also disclosed.
  • Non-Patent Document 1 polysilamine was doped with phosphoric acid (see Non-Patent Document 2), polyacrylamide was sulfuric acid, Or phosphoric acid doped (see Non-patent Document 3), Polybenzimidazole doped with phosphoric acid (see Patent Document 7), Sulfony-polyether sulfone with polybenzimidazole added (Non-patent) (Refer to Reference 4.)
  • Non-Patent Document 1 polysilamine was doped with phosphoric acid
  • Patent Document 3 polyacrylamide was sulfuric acid, Or phosphoric acid doped
  • Patent Document 7 Polybenzimidazole doped with phosphoric acid
  • Patent Document 7 Sulfony-polyether sulfone with polybenzimidazole added (Non-patent) (Refer to Reference 4.)
  • there are many problems such as the dopant flowing down and not showing sufficient ionic conductivity.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-81220
  • Patent Document 2 Patent WO00,54351
  • Patent Document 3 Japanese Patent Laid-Open No. 11-302410
  • Patent Document 4 Japanese Patent Laid-Open No. 2003-157862
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2001-135328
  • Patent Document 6 JP-A-2005-71961
  • Patent Document 7 Japanese Patent Publication No. 11-503262
  • Non-Patent Document 2 K. Tsuruhara, M. Rikukawa, K. Sassemble, N. Ogata, Y. Nagasaki, and M. Kato, E lectrochim 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 Ionics, 125, 243 (19
  • the present invention was made in order to solve the current problems of the PFS polymer hydration film, the PFS modified film, and various electrolyte films as the solid polymer electrolyte film for DMFC as described above.
  • Another object of the present invention is to provide a solid polymer electrolyte membrane excellent in methanol permeation-preventing property while maintaining high proton conductivity, and a fuel cell including the solid polymer electrolyte membrane.
  • the present invention is as follows.
  • At least one of a vinyl monomer having a basic group and a crosslinkable vinyl monomer has an aromatic ring or a heterocyclic ring, and these monomers are impregnated into a polyolefin porous membrane and polymerized, followed by sulfonation.
  • a solid polymer electrolyte membrane obtained by treatment.
  • the solid polymer electrolyte membrane according to the above item 1 which is a vinyl monomer having 2 basic groups and having 2 bullypyridine or 4 vinyl pyridine.
  • the molar ratio of the charge when impregnating the vinyl monomer having a basic group and the crosslinkable vinyl monomer (the number of moles of a bull monomer having a basic group) 2.
  • the polymer electrolyte membrane according to 1 above, wherein the number of moles of monomer) force ranges from 20Z80 to 90Z10.
  • 100 parts by mass of the polyolefin porous membrane contains 30 to L00 parts by mass of a polymer component composed of the basic monomer-containing monomer, the cross-linkable butyl monomer, and the third monomer. 8. The solid polymer electrolyte membrane according to 7 above.
  • a fuel cell comprising the solid polymer electrolyte membrane according to 1 above, and a positive electrode and a negative electrode sandwiching the solid polymer electrolyte membrane.
  • FIG. 1 is a schematic configuration diagram showing an example of a fuel cell using a solid polymer electrolyte membrane.
  • the solid polymer electrolyte membrane of the present invention is obtained by impregnating a polyolefin porous membrane with a vinyl monomer having a basic group and a crosslinkable butyl monomer, followed by polymerization and then sulfonation treatment. Obtained. At least one of the vinyl monomer having a basic group and the crosslinkable vinyl monomer has an aromatic ring or a heterocyclic ring.
  • Examples of the vinyl monomer having a basic group include acrylamide, arylamine, berylpyrrolidone, belimidazole, aminoacrylamide, belaminosulfone, bilyridine, dimethylaminoethyl (meth) acrylate and beercaprolatatam. , Berylcarbazole, vinyldiaminotriazine, ethyleneimine, and the like that contain a nitrogen atom in the molecule.
  • 2-bulupyridine, 4-bulupyridine or a mixture thereof is preferable.
  • crosslinkable butyl monomer examples include dibutyl benzene, tetraethylene glycol dimetatalylate, methylene bisacrylamide, ethylene glycol dimetatalylate, diethylene glycol dimetatalylate, triethylene glycol dimetatalylate, and nonaethylene.
  • examples include dibule compounds such as glycol dimetatalylate. In particular, dibulene benzene is preferred.
  • At least one of the vinyl monomer having a basic group and the cross-linkable vinyl monomer has an aromatic ring or a heterocyclic ring.
  • a third monomer copolymerizable with these monomers and a solvent may be added as necessary.
  • Examples of the third monomer include styrene, urnaphthalene, sodium acrylamide-butyrylsulfonate, sodium vinylsulfonate, and the like.
  • Examples of the solvent include toluene, xylene, dimethyl sulfoxide, dimethylformamide, alcohols, and the like.
  • a so-called plasticizer can also be used as a solvent.
  • powers such as tributyl acetyl citrate, dibutyl phthalate, dioctyl phthalate, dibutyl adipate, and tributyl daricerol are not limited to these. What is necessary is just to select suitably considering a boiling point, a viscosity, the impregnation property to a polyolefin membrane, etc.
  • the molar ratio of the charge when impregnating the vinyl monomer having a basic group and the crosslinkable vinyl monomer (the number of moles of the bull monomer having a basic group) The number of moles) is preferably in the range of 20/80 to 90/10. By being in the strong range, good film-forming property is shown, and good proton conductivity and excellent methanol permeation-preventing property can be expressed through a sulfone cocoon process described later.
  • the molar ratio is more preferably in the range of 70/30 to 40/60, more preferably in the range of 60Z40 to 50Z50.
  • the ratio of the total number of moles (Q) and the third monomer (Q) to the number of moles (R) of the crosslinkable butyl monomer, that is, (P + Q) ZR is in the range of 20 ⁇ 80 to 90 ⁇ 10, and the base It is preferable that the molar ratio (PZQ) of the butyl monomer having a functional group and the third monomer is in the range of 10Z90 to 99Zl.
  • Copolymerization of a vinyl monomer having a basic group and a crosslinkable butyl monomer can be initiated by heat, light, electron beam, or the like.
  • a radical polymerization initiator, a cationic polymerization initiator or a cation polymerization initiator can be used.
  • a radical polymerization initiator is preferred.
  • peroxide compounds with high hydrogen abstraction ability are used, in addition to the polymerization reaction between the butyl monomer having a basic group and the crosslinkable butyl monomer, a crosslinked structure is also formed with the porous membrane made of polyolefin.
  • a radical initiator for example, an organic peracid salt described in a catalog of Nippon Oil & Fats Co., Ltd. can be used.
  • t-butyl peroxide 2-ethylhexyl carbonate and benzoyl peroxide are preferable.
  • the addition amount of the polymerization initiator depends on the polymerization conditions, but is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 100 parts by weight of the total amount of raw material monomers used. Is 0.05 to 2 parts by weight.
  • the polymerization temperature is 0 ° C to 120 ° C, preferably 20 ° C to 100 ° C, more preferably 30 ° C to 80 ° C. Consider the monomer composition, physical properties of the resulting polymer, process time, etc. And choose as appropriate.
  • polyolefin is used as a raw material for the porous membrane used in the present invention.
  • forces including polyethylene, polypropylene, polystyrene and the like are not limited to these.
  • polyethylene particularly preferably ultrahigh molecular weight polyethylene is used. I can.
  • the weight average molecular weight of the polyolefin is 50,000 or more, preferably 1 million or more, more preferably 5 million or more.
  • the average pore diameter of the porous porous polyolefin membrane used in the present invention is 0.001 to 5 ⁇ m, preferably 0.001 to 1 / ⁇ ⁇ , and more preferably 0.00 to 0.05. It is.
  • the porosity of the polyolefin porous membrane used in the present invention is 20 to 60%, preferably 30 to 50%, more preferably 35 to 45%.
  • the thickness of the porous polyolefin membrane used in the present invention is usually 1 to 300 m, preferably 5 to: LOO ⁇ m, more preferably 10 to 50 ⁇ m.
  • the air permeability of the polyolefin porous membrane used in the present invention is 100 to 900 seconds ZlOOml, preferably 150 to 750 seconds ZlOOml, more preferably 200 to 650 seconds ZlOOml.
  • porous membrane made of polyolefin used in the present invention examples include Hypore (registered trademark) manufactured by Asahi Kasei Chemicals Co., Ltd., Solpore (registered trademark), Solfil (registered trademark), Mitsui Examples include ESPOAR (registered trademark) manufactured by Gaku Co., Ltd., SETILA (registered trademark) manufactured by TonenGeneral Sekiyu KK, and YUPO (registered trademark) manufactured by YUPO Corporation.
  • the polyolefin porous membrane used in the present invention is preferably hydrophilized prior to impregnation described later!
  • a known method can be applied to the hydrophilization treatment, and the hydrophilization treatment is not limited.
  • the permeability of the raw material monomer to the porous membrane can be further enhanced in the impregnation described later.
  • the polyolefin porous membrane is impregnated with a raw material composition containing a butyl monomer having a basic group, a cross-linkable vinyl monomer, and a polymerization initiator.
  • the impregnation treatment is performed by a known method and is not limited.
  • a porous membrane made of polyolefin is immersed in the raw material composition, and is sandwiched between release films such as PET to remove excess raw material composition.
  • release films such as PET
  • the impregnation treatment is usually performed under normal temperature and normal pressure, but may be performed under pressure or under reduced pressure as necessary.
  • polymerization is performed.
  • the impregnated porous membrane is sandwiched between glass plates through the above release film and polymerized by heating in a nitrogen atmosphere.
  • the polymerization conditions may be appropriately selected in consideration of the type of polymerization initiator and the composition of the raw material composition.
  • the film obtained by polymerization is immersed in a commonly used solvent such as acetone and methanol to remove the solvent and unreacted substances, and then dried.
  • a commonly used solvent such as acetone and methanol
  • sulfonation treatment After drying, sulfonation treatment is performed.
  • a general method using fuming sulfuric acid or black sulfuric acid can be applied to the sulfonation treatment.
  • the rate of weight increase due to sulfonation treatment ((weight of polymer after sulfonation treatment-weight of polymer before sulfonation treatment) Z weight of polymer before sulfonation treatment X 100) is in the range of 10-80% preferable. Within this range, the balance of proton conductivity, methanol permeation blocking property and mechanical strength of the solid polymer electrolyte membrane can be maintained.
  • the weight increase rate due to the sulfonation treatment is more preferably 20 to 70%, particularly preferably 30 to 60%.
  • a solid polymer electrolyte membrane in which an acidic group and a basic group coexist, more specifically, an acidic group and a basic group.
  • a solid polymer membrane can be obtained in which salts are formed within and between molecules of acidic and basic groups.
  • the PFS polymer membrane is a force that requires water to intervene because protons are transferred in the form of hydrogen ions.
  • the Grotthuss Mechanism does not require water between the salts in the electrolyte membrane of the present invention. Protons are thought to be transmitted. Therefore, protons are transferred smoothly between adjacent salts toward the negative electrode and the positive electrode.
  • the salt since the salt has higher affinity with water than methanol, it exhibits excellent methanol permeation-preventing properties. By this action, water generated on the positive electrode side by power generation can be guided to the negative electrode side, and power generation can be continued by supplementing water necessary for the reaction on the negative electrode side. As a result, it is possible to use high-concentration methanol as fuel, which is extremely difficult with conventional PFS polymer membranes.
  • the gas diffusion layer 3 may be provided on the surfaces of the positive electrode 2a and the negative electrode 2b. By this gas diffusion layer 3, gases such as methanol and oxygen used for power generation are diffused and uniformly distributed on the surfaces of the positive electrode 2a and the negative electrode 2b.
  • the proton conductivity of the solid polymer electrolyte membrane of the present invention was measured using an impedance analyzer SI1260 manufactured by Solartron, UK, at 25 ° C and 100% humidity, 3 hours after the sample was mounted in the measurement cell. High frequency impedance measurements were made. Next, the direct current component R was read from the Col Col plot, and the proton conductivity ( ⁇ cm 2 ) was calculated.
  • the methanol permeation rate of the solid polymer electrolyte membrane of the present invention was measured according to the following method.
  • the obtained solid polymer electrolyte membrane was sandwiched in the center of the communication tube, 100 ml of 30% methanol aqueous solution was charged on one side, and 100 ml of ion exchange water on the other side, and immersed in a constant temperature water bath at 40 ° C. After 3 hours, methanol permeating into the water side was quantified by gas chromatography and the methanol permeation rate (mg / cm 2 / min) was calculated.
  • the obtained film was immersed in acetone to remove unreacted materials, tributyl acetyl citrate, xylene and the like, and then sufficiently dried.
  • the obtained film was a uniform translucent film with no repellent spots.
  • the membrane is then immersed in fuming sulfuric acid (SO concentration: 2 to 3 wt%) and reacted at 60 ° C for 90 minutes.
  • SO concentration 2 to 3 wt%
  • a polyethylene porous membrane that has been hydrophilized by corona discharge treatment (“Hypore N9420G” (registered trademark) manufactured by Asahi Kasei Chemicals Co., Ltd.) is impregnated with the monomer solution B, sandwiched between PET films, and further sandwiched between glass plates.
  • the reaction was carried out at 80 ° C for 20 hours in a nitrogen atmosphere.
  • the obtained film was immersed in acetone to remove unreacted materials, tributyl acetyl citrate, xylene and the like, and then sufficiently dried.
  • the obtained film was a uniform translucent film with no repellent spots.
  • the membrane is then immersed in fuming sulfuric acid (SO concentration: 2 to 3 wt%) and reacted at 60 ° C for 90 minutes.
  • SO concentration 2 to 3 wt%
  • the obtained film was immersed in acetone to remove unreacted materials, tributyl acetyl citrate, xylene and the like, and then sufficiently dried.
  • the obtained film was a uniform translucent film with no repellent spots.
  • the membrane is then immersed in fuming sulfuric acid (SO concentration: 3-4 wt%) and reacted at 70 ° C for 85 minutes.
  • SO concentration 3-4 wt%
  • a polyethylene porous membrane that has been hydrophilized by corona discharge treatment (“Hypore NA635" (registered trademark) manufactured by Asahi Kasei Chemicals Co., Ltd.) is impregnated with the monomer solution C, sandwiched between PET films, and further sandwiched between glass plates.
  • the reaction was carried out in a nitrogen atmosphere for 20 hours at 80 ° C.
  • the obtained film was a uniform translucent film with no repellency spots.
  • the obtained film was immersed in acetone to remove unreacted materials, tributyl acetyl citrate, xylene and the like, and then sufficiently dried.
  • the membrane is then immersed in fuming sulfuric acid (SO concentration: 2 to 3 wt%) and reacted at 70 ° C for 30 minutes.
  • SO concentration 2 to 3 wt%
  • the fuel cell assembly kit manufactured by Chemix Co., Ltd. Pem Master PEM— 004DM incorporates the solid polymer electrolyte membrane obtained in Example 1 instead of the naphthion (registered trademark) membrane, and 30% methanol is used as the fuel tank. (Volume: 4 ml). As a result, power was generated until the fuel was exhausted, and the motor was rotated.
  • a negative electrode catalyst prepared by mixing a carbon material carrying a ruthenium monoplatinum catalyst and a perfluorosulfonic acid ion-exchanged resin (manufactured by DuPont, Nafion (registered trademark)) and applying it to a carbon paper.
  • a positive electrode side catalyst layer prepared by mixing a layer, and a carbon material carrying a platinum catalyst and a perfluorosulfonic acid ion exchange resin (manufactured by DuPont, Naphion (registered trademark)) and applying it to carbon paper,
  • a fuel cell was fabricated by sandwiching the solid polymer electrolyte membrane obtained in Example 1 with these two catalyst layers. When the temperature of the fuel cell was kept at 40 ° C., 10% methanol was supplied to the negative electrode side and air was supplied to the positive electrode side, a maximum output of 34 mWZcm 2 was obtained.
  • a carbon paper carrying a ruthenium monoplatinum catalyst and a perfluorosulfonic acid ion-exchanged resin (manufactured by DuPont, Nafion (registered trademark)) solution are mixed to obtain a carbon paper.
  • the produced positive electrode side catalyst layer was produced, and a fuel cell was produced by sandwiching a naphthion 117 (registered trademark) membrane between these two catalyst layers. When the temperature of this fuel cell was kept at 40 ° C., 10% methanol was supplied to the negative electrode side and air was supplied to the positive electrode side, the maximum output llmWZcm 2 was obtained.
  • the solid polymer electrolyte membrane of the present invention has both high proton conductivity and excellent methanol permeation inhibiting properties.
  • the electrolyte membrane is useful for fuel cells such as DMFC and PEFC.
  • the production of the solid polymer electrolyte membrane of the present invention is simple and can be produced at low cost.

Abstract

La présente invention concerne une membrane à électrolyte polymère solide dont l'imperméabilité au méthanol est excellente, tout en maintenant une conductivité de protons élevée. Elle concerne également une pile à combustible comprenant une telle membrane à électrolyte polymère solide. Elle concerne spécifiquement une membrane à électrolyte polymère solide qui est obtenue en imprégnant une membrane poreuse polyoléfine d'un monomère de vinyle comportant un groupe de base et un monomère de vinyle réticulable, au moins l'un des monomères comportant un cycle aromatique ou un cycle hétérocyclique, puis en polymérisant les monomères, et en soumettant la membrane ainsi réalisée à un traitement de sulfonation. L'invention concerne aussi spécifiquement une pile à combustible comprenant ladite membrane à électrolyte polymère solide, et une électrode positive et une électrode négative entre lesquelles est intercalée la membrane à électrolyte polymère solide.
PCT/JP2007/063343 2006-07-06 2007-07-04 Membrane et pile à combustible à électrolyte polymère solide WO2008004567A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008523700A JPWO2008004567A1 (ja) 2006-07-06 2007-07-04 固体高分子電解質膜および燃料電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-186532 2006-07-06
JP2006186532 2006-07-06

Publications (1)

Publication Number Publication Date
WO2008004567A1 true WO2008004567A1 (fr) 2008-01-10

Family

ID=38894534

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/063343 WO2008004567A1 (fr) 2006-07-06 2007-07-04 Membrane et pile à combustible à électrolyte polymère solide

Country Status (2)

Country Link
JP (1) JPWO2008004567A1 (fr)
WO (1) WO2008004567A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11135137A (ja) * 1997-10-31 1999-05-21 Asahi Glass Co Ltd 固体高分子電解質型メタノール燃料電池
JP2004217921A (ja) * 2002-12-26 2004-08-05 Tokuyama Corp イオン交換膜及びその製造方法
JP2005032535A (ja) * 2003-07-11 2005-02-03 Tokuyama Corp 接合体
JP2005032536A (ja) * 2003-07-11 2005-02-03 Tokuyama Corp 接合体の製造方法
JP2005332800A (ja) * 2004-04-23 2005-12-02 Sekisui Chem Co Ltd 直接メタノール型燃料電池用プロトン伝導性膜
JP2006160837A (ja) * 2004-12-03 2006-06-22 Toagosei Co Ltd 電解質膜の製造方法
JP2006164628A (ja) * 2004-12-03 2006-06-22 Toagosei Co Ltd 電解質膜および燃料電池
JP2006172764A (ja) * 2004-12-13 2006-06-29 Toagosei Co Ltd 電解質膜の製造方法
JP2006172765A (ja) * 2004-12-13 2006-06-29 Toagosei Co Ltd 電解質膜の連続製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11135137A (ja) * 1997-10-31 1999-05-21 Asahi Glass Co Ltd 固体高分子電解質型メタノール燃料電池
JP2004217921A (ja) * 2002-12-26 2004-08-05 Tokuyama Corp イオン交換膜及びその製造方法
JP2005032535A (ja) * 2003-07-11 2005-02-03 Tokuyama Corp 接合体
JP2005032536A (ja) * 2003-07-11 2005-02-03 Tokuyama Corp 接合体の製造方法
JP2005332800A (ja) * 2004-04-23 2005-12-02 Sekisui Chem Co Ltd 直接メタノール型燃料電池用プロトン伝導性膜
JP2006160837A (ja) * 2004-12-03 2006-06-22 Toagosei Co Ltd 電解質膜の製造方法
JP2006164628A (ja) * 2004-12-03 2006-06-22 Toagosei Co Ltd 電解質膜および燃料電池
JP2006172764A (ja) * 2004-12-13 2006-06-29 Toagosei Co Ltd 電解質膜の製造方法
JP2006172765A (ja) * 2004-12-13 2006-06-29 Toagosei Co Ltd 電解質膜の連続製造方法

Also Published As

Publication number Publication date
JPWO2008004567A1 (ja) 2009-12-03

Similar Documents

Publication Publication Date Title
US7534515B2 (en) Acid-base proton conducting polymer blend membrane
Luo et al. Preparation and characterization of Nafion/SPEEK layered composite membrane and its application in vanadium redox flow battery
EP1630890B1 (fr) Membrane à électrolyte polymère et pile à combustible la contenant
KR102466595B1 (ko) 높은 선택성 및 높은 강도를 위한 고도로 강화된 이오노머 막
US8372558B2 (en) Highly proton-conductive polymer electrolyte membranes that excel in mechanical strength and a process for producing the same
Gloukhovski et al. Understanding methods of preparation and characterization of pore-filling polymer composites for proton exchange membranes: a beginner’s guide
US20070166592A1 (en) Polymer electrolyte membrane, method of preparing the same and fuel cell employing the same
JP2010538416A (ja) 高分子形燃料電池に用いられるプロトン伝導性高分子電解質膜
CA2686279A1 (fr) Methode de production d'une structure d'electrode pour une pile a combustible polymere solide
KR100914340B1 (ko) 고 수소 이온 전도성 연료전지용 비닐술폰산 가교 고분자전해질 복합막의 제조방법 및 이를 이용한 연료전지
Higa et al. Characteristics and direct methanol fuel cell performance of polymer electrolyte membranes prepared from poly (vinyl alcohol-b-styrene sulfonic acid)
EP3229302A1 (fr) Membrane électrolytique polymère
Kuzume et al. Characterisation of PAMPS–PSS pore-filling membrane for direct methanol fuel cell
JP3896105B2 (ja) 燃料電池用電解質膜、及び燃料電池
JP5189394B2 (ja) 高分子電解質膜
JP2005327703A (ja) 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
Othman et al. Recent development of polymer electrolyte membranes for direct methanol fuel cell application–a review
EP2053673A1 (fr) Electrode pour pile à combustible, son processus de fabrication, et pile à combustible
KR20220145751A (ko) 신규 지방족 사슬 함유 폴리(알킬-아릴 피페리디늄) 중합체 이오노머, 음이온교환막, 복합막 및 이의 제조방법
WO2008004567A1 (fr) Membrane et pile à combustible à électrolyte polymère solide
KR100880092B1 (ko) 탄화수소계 고분자 전해질막 표면 개질
JP2007115535A (ja) 電解質膜およびその製造方法
JP2006024552A (ja) 固体高分子電解質膜および燃料電池
KR20110090051A (ko) 퍼플루오로사이클로부탄기를 포함하는 브랜치된 술폰화 공중합체, 이의 제조방법 및 이를 이용한 전해질막
Choudhury et al. Studies on the Preparation and Characterization of Poly (vinyl alcohol-co-styrenesulfonicacid)-Based Proton Exchange Membranes for Direct Methanol Fuel Cell

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07768113

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008523700

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 07768113

Country of ref document: EP

Kind code of ref document: A1