WO2003007411A2 - Procede de production d'une membrane electrolyte en polymere polymerisee par plasma et membrane de polyazol revetue de plasma - Google Patents

Procede de production d'une membrane electrolyte en polymere polymerisee par plasma et membrane de polyazol revetue de plasma Download PDF

Info

Publication number
WO2003007411A2
WO2003007411A2 PCT/EP2002/007734 EP0207734W WO03007411A2 WO 2003007411 A2 WO2003007411 A2 WO 2003007411A2 EP 0207734 W EP0207734 W EP 0207734W WO 03007411 A2 WO03007411 A2 WO 03007411A2
Authority
WO
WIPO (PCT)
Prior art keywords
plasma
acid
polyazole
aromatic
different
Prior art date
Application number
PCT/EP2002/007734
Other languages
German (de)
English (en)
Other versions
WO2003007411A3 (fr
Inventor
Jörg Müller
Laurent Mex
Original Assignee
Mueller Joerg
Laurent Mex
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 Mueller Joerg, Laurent Mex filed Critical Mueller Joerg
Priority to JP2003513069A priority Critical patent/JP2005520001A/ja
Priority to US10/482,354 priority patent/US20040186189A1/en
Priority to AU2002328339A priority patent/AU2002328339A1/en
Priority to CA002448447A priority patent/CA2448447A1/fr
Priority to EP02762348A priority patent/EP1497882A2/fr
Priority to KR10-2003-7016749A priority patent/KR20040014572A/ko
Publication of WO2003007411A2 publication Critical patent/WO2003007411A2/fr
Publication of WO2003007411A3 publication Critical patent/WO2003007411A3/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/127—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction using electrical discharge or plasma-polymerisation
    • 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
    • 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
    • H01M8/1023—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
    • 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
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • 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
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • 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
    • 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 invention relates to a process for the production of polymer electrolyte membranes by means of plasma-assisted deposition from the gas phase, which achieves a significant simplification compared to the prior art by the choice of its starting materials.
  • the invention further relates to a plasma-coated polyazole membrane.
  • Plasma-polymerized layers generally have a high and also adjustable degree of crosslinking, which leads to a high chemical and thermal resistance (see, for example: R. Hartmann: “Plasma polymodification of plastic surfaces", Techn. Rundschau 17 (1988), pages 20-23; A. Brunold et al .: “Modification of polymers in low pressure plasma ", part 2, mo 51 (1997), pages 81-84).
  • ion-conducting polymer membranes can be produced with this method, which are characterized by their resistance and the high degree of crosslinking due to their barrier effect with respect to gas or Offer liquid permeation for use in fuel cells, especially direct methanol fuel cells, or electrolysis cells.
  • the deposition technology used enables the production of thin membranes (a few 10 nm to a few 10 ⁇ m), which are deposited in particular for use in miniaturized fuel cell systems for portable applications (see, for example, DE 196 24 887 A1, DE 199 14 681 A1) or as barrier layers conventional membranes (DE 199 14 571 A1), such as phosphoric acid-doped polybenzimidazole membranes or membranes containing sulfonic acid, are of interest.
  • the plasma polymerization according to the invention of ion-conducting layers with the use of carbon compounds, preferably alkenes and alkynes, or fluorocarbon compounds, preferably fluorinated alkenes, in combination with water offers a significant simplification in process control and a significant reduction in production costs.
  • the fragmentation of the water in the plasma leads to the formation of OH radicals, as a result of which the carboxyl groups necessary for ionic conductivity are only formed during layer growth.
  • the use of commercially available liquid mass flow controllers means that the evaporator required for other acid compounds is eliminated.
  • the high vapor pressure of the water also allows separation at room temperature, while with the acid compounds mentioned, heating of the gas supply from the evaporator to the reactor and the electrodes is necessary in order to prevent condensation of the acid compounds in these areas.
  • the combination with catalyst layers produced in thin-layer processes eg cathode sputtering or plasma-assisted deposition from the gas phase
  • catalyst layers produced in thin-layer processes eg cathode sputtering or plasma-assisted deposition from the gas phase
  • porous conductive ones are suitable for their manufacture
  • Contact layers on (DE 199 14 681 A) can be carried out in a suitable reactor, which allows both sputtering and gas phase deposition, or in interconnected separate reactors, in each of which a component of the membrane electrode assembly is deposited in a thin-film process and transported between the reactors in a vacuum, be performed.
  • a stationary deposition process of the plasma-polymerized electrolytes for example for the coating of suitably structured glass or silicon substrates, or a continuous process, in the case of large quantities or when deposition on a suitable film, can be advantageous.
  • the method described above is particularly suitable for the production of plasma-coated polyazole membranes.
  • Acid-doped polyazole membranes can be used in a variety of ways due to their excellent chemical, thermal and mechanical properties and are particularly suitable as polymer electrolyte membranes (PEM) in so-called PEM fuel cells.
  • PEM polymer electrolyte membranes
  • the basic polyazole membranes are doped with concentrated phosphoric acid or sulfuric acid and act as proton conductors and separators in so-called polymer electrolyte membrane fuel cells (PEM fuel cells).
  • PEM fuel cells polymer electrolyte membrane fuel cells
  • such polymer electrolyte membranes - processed into membrane electrode assemblies (MEE) - can be used in fuel cells at continuous operating temperatures above 100 ° C, in particular above 120 ° C.
  • This high continuous operating temperature allows the activity of the precious metal-based catalysts contained in the membrane electrode assembly (MEE) to be increased.
  • the reformer gas contains significant amounts of carbon monoxide, which usually have to be removed by complex gas processing or gas cleaning.
  • Polyazoles contain recurring azole units of the general formula (I) and / or (II) and / or (III) and / or (IV) and / or (V) and / or (VI) and / or (VII) and / or ( VIII) and / or (IX) and / or (X) and / or (XI) and / or (XII) and / or (XIII) and / or (XIV) and / or (XV) and / or (XVI) and / or (XVI) and / or (XVII) and / or (XVIII) and / or (XIX) and / or (XX) and / or (XXI) and / or (XVIII) and / or (XIX) and / or (XX) and / or (XXI) and / or (XXII) and / or (XXII))
  • Ar are the same or different and, for a tetra-bonded aromatic or heteroaromatic group which may be mono- or polynuclear, Ar 1 are the same or different and for a divalent aromatic or heteroaromatic group which may be mono- or polynuclear, Ar 2 are the same or different Ar 3 are the same or different for a two or three-membered aromatic or heteroaromatic group, which may be mononuclear or polynuclear, and for a tridentic aromatic or heteroaromatic group, which may be mononuclear, Ar 4 are the same or different and for a three-membered aromatic or heteroaromatic group which can be mono- or polynuclear, Ar 5 are the same or different and for a tetra-aromatic or heteroaromatic group which can be mono- or polynuclear, Ar 6 are the same or different and for a double-bonded aromatic or heteroaromatic group, which can be mononuclear or polynuclear, Ar 7 identical or ve
  • Amino group which has a hydrogen atom, a group having 1-20 carbon atoms, preferably a branched or unbranched
  • aromatic or heteroaromatic groups are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, pyrol, benzene, pyrrole, pyrrole, pyrrole, anthracene Benzooxathiadiazol, Benzooxadiazol, benzopyridine, benzopyrazine, Benzopyrazidin, benzopyrimidine, benzopyrazine
  • the substitution pattern of Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 is arbitrary, in the case of phenylene, for example, Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 are ortho-, meta- and para-phenylene. Particularly preferred groups are derived from benzene and biphenylene, which may also be substituted.
  • Preferred alkyl groups are short-chain alkyl groups with 1 to 4 carbon atoms, such as. B. methyl, ethyl, n- or i-propyl and t-butyl groups.
  • Preferred aromatic groups are phenyl or naphthyl groups.
  • the alkyl groups and the aromatic groups can be substituted.
  • Preferred substituents are halogen atoms such as. B. fluorine, amino groups, hydroxy groups or short-chain alkyl groups such as. B. methyl or ethyl groups.
  • the polyazoles can also have different recurring units which differ, for example, in their X radical. However, it preferably has only the same X radicals in a recurring unit.
  • Further preferred polyazole polymers are polyimidazoles, polybenzthiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxalines, polythiadiazoles poly (pyridines), poly (pyrimidines), and poly (tetrazapyrenes).
  • the polymer containing recurring azole units is a copolymer or a blend which contains at least two units of the formulas (I) to (XXII) which differ from one another.
  • the polymers can be present as block copolymers (diblock, triblock), statistical copolymers, periodic copolymers and / or alternating polymers.
  • the polymer containing recurring azole units is a polyazole which contains only units of the formula (I) and / or (II).
  • the number of repeating azole units in the polymer is preferably an integer greater than or equal to 10.
  • Particularly preferred polymers contain at least 100 repeating azole units.
  • polymers containing recurring benzimidazole units are preferred.
  • Some examples of the extremely useful polymers containing recurring benzimidazole units are represented by the following formulas:
  • n and m is an integer greater than or equal to 10, preferably greater than or equal to 100.
  • Preferred polyazoles but especially the polybenzimidazoles, are distinguished by a high molecular weight. Measured as intrinsic viscosity, this is at least 1.0 dl / g, preferably at least 1.2 1 dl / g.
  • the preparation of such polyazoles is known, in which one or more aromatic tetra-amino compounds with one or more aromatic carboxylic acids or their esters, which contain at least two acid groups per carboxylic acid monomer, are reacted in the melt to form a prepolymer.
  • the resulting prepolymer solidifies in the reactor and is then mechanically crushed.
  • the powdery prepolymer is usually end-polymerized in a solid-phase polymerization at temperatures of up to 400 ° C.
  • the preferred aromatic carboxylic acids include, among others, dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids or their esters or their anhydrides or their acid chlorides.
  • aromatic carboxylic acids also includes heteroaromatic carboxylic acids.
  • the aromatic dicarboxylic acids are preferably isophthalic acid, terephthalic acid, phthalic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 5-aminoisophthalic acid, 5-N, N-dimethylaminoisophthalic acid, 5-N, N-diethylaminoisinoamino - Dihydroxy terephthalic acid, 2,6-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid.
  • C5-C12 aryl esters or their acid anhydrides or their acid chlorides are preferably 1,3,5-benzene-tricarboxylic acid (Trimesic acid), 1,2,4-benzene-tricarboxylic acid (Trimellitic acid),
  • C12 aryl esters or their acid anhydrides or their acid chlorides are preferably 3,5,3 ', 5'-biphenyltetracarboxylic acid, 1, 2,4,5-benzenetetracarboxylic acid,
  • Benzophenonetetracarboxylic acid 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2, 2', 3, 3'- Biphenyltetracarboxylic acid, 1, 2,5,6-naphthalenetetracarboxylic acid, 1, 4,5,8-naphthalenetetracarboxylic acid.
  • heteroaromatic carboxylic acids used are preferably heteroaromatic dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids or their esters or their anhydrides.
  • Heteroaromatic carboxylic acids are understood to mean aromatic systems which contain at least one nitrogen, oxygen, sulfur or phosphorus atom in the aromatic.
  • pyridine-2,5-dicarboxylic acid pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5-pyridinedicarboxylic acid, 3.5 -Pyrazole dicarboxylic acid, 2,6-pyrimidine dicarboxylic acid, 2,5-pyrazine dicarboxylic acid, 2,4,6-pyridine tricarboxylic acid, benzimidazole-5,6-dicarboxylic acid.
  • C1-C20 alkyl esters or C5-C12 aryl esters or their acid anhydrides or their acid chlorides.
  • the content of tricarboxylic acid or tetracarboxylic acids is between 0 and 30 mol%, preferably 0.1 and 20 mol%, in particular 0.5 and 10 mol%.
  • aromatic and heteroaromatic diaminocarboxylic acids used are preferably diaminobenzoic acid and its mono- and dihydrochloride derivatives.
  • Mixtures of at least 2 different aromatic carboxylic acids are preferred. Mixtures which contain not only aromatic carboxylic acids but also heteroaromatic carboxylic acids are particularly preferred.
  • the mixing ratio of aromatic carboxylic acids to heteroaromatic carboxylic acids is between 1:99 and 99: 1, preferably 1:50 to 50: 1.
  • This mixture is in particular a mixture of N-heteroaromatic dicarboxylic acids and aromatic dicarboxylic acids.
  • Non-limiting examples of this are isophthalic acid, terephthalic acid, phthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-dihydroxyisophthalic acid, 4,6- Dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid.
  • the preferred aromatic tetraamino compounds include, among others, 3,3 ', 4,4'-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine, 1, 2,4,5-tetraaminobenzene, 3,3', 4 , 4'-tetraaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminobenzophenone, 3,3 ', 4,4'-tetraaminodiphenylmethane and 3,3', 4,4 '-Tetraaminodiphenyldimethylmethane and their salts, especially their mono-, di-, tri- and tetrahydrochloride derivatives.
  • Preferred polybenzimidazoles are commercially available from Celanese AG under the trade name ⁇ Celazole.
  • a blend which contains further polymers can also be used.
  • the blend component essentially has the task of improving the mechanical properties and reducing the material costs.
  • a preferred blend component is polyethersulfone as described in German patent application No. 10052242.4.
  • the polyazole is dissolved in polar, aprotic solvents such as dimethylacetamide (DMAc) in a further step and a film is produced using conventional methods.
  • polar, aprotic solvents such as dimethylacetamide (DMAc)
  • the film obtained in this way can be treated with a washing liquid.
  • This washing liquid is preferably selected from the group of alcohols, ketones, alkanes (aliphatic and cycloaliphatic), ethers (aliphatic and cycloaliphatic), esters, carboxylic acids, where the above group members can be halogenated, water, inorganic acids (such as H 3 PO 4 , H 2 S0 4 ) and mixtures thereof.
  • C 1 -C 10 alcohols C 2 -C 5 ketones, Ci-C-io-alkanes (aliphatic and cycloaliphatic), C 2 -C 6 ethers (aliphatic and cycloaliphatic), C 2 -C 5 esters, C1 -C 3 carboxylic acids, dichloromethane, water, inorganic acids (such as H3PO 4 , H 2 S0 4 ) and mixtures thereof.
  • water is particularly preferred.
  • the film can be dried to remove the washing liquid. Drying is dependent on the partial vapor pressure of the selected treatment liquid. Drying is usually carried out at normal pressure and temperatures between 20 ° C and 200 ° C. A more gentle drying can also be done in a vacuum. Instead of drying, the membrane can also be dabbed off, thus removing excess treatment liquid. The order is not critical.
  • the polymer film can have further modifications, for example by crosslinking as in German patent application No. 10110752.8 or in WO 00/44816.
  • the polymer film used contains a basic polymer and at least one blend component and additionally a crosslinking agent as described in German patent application No. 10140147.7.
  • the polyazole-containing polymer membranes can also be used as described in German patent applications No. 10117686.4, 10144815.5, 10117687.2.
  • the thickness of the polyazole films can be in a wide range.
  • the thickness of the polyazole film before doping with acid is preferably in the range from 5 ⁇ m to 2000 ⁇ m, particularly preferably 10 ⁇ m to 1000 ⁇ m, without any intention that this should impose a restriction.
  • acids include all known Lewis and Bronsted acids, preferably inorganic Lewis and Bronsted acids.
  • heteropolyacids denote inorganic polyacids with at least two different central atoms, each of which consists of weak, polybasic oxygen acids of a metal (preferably Cr, Mo, V, W) and a non-metal (preferably As, I, P, Se, Si, Te) arise as partially mixed anhydrides. They include, among others, 12-molybdate phosphoric acid and 12-tungstophosphoric acid.
  • the conductivity of the polyazole film can be influenced via the degree of doping.
  • the conductivity increases with increasing dopant concentration until a maximum value is reached.
  • the degree of doping is stated as mole of acid per mole of repeating unit of the polymer. In the context of the present invention, a degree of doping between 3 and 30, in particular between 5 and 18, is preferred.
  • Particularly preferred dopants are sulfuric acid and phosphoric acid.
  • a very particularly preferred dopant is phosphoric acid (H 3 P0 4 ). Highly concentrated acids are generally used here. According to a particular aspect of the present invention, the concentration of the phosphoric acid is at least 50% by weight, in particular at least 80% by weight, based on the weight of the dopant.
  • doped polyazole films can also be obtained by a process comprising the steps comprising the steps I) dissolving the polyazole polymer in polyphosphoric acid,
  • step II heating the solution obtainable according to step A) under inert gas to temperatures of up to 400 ° C.
  • step IV Treatment of the membrane formed in step III) until it is self-supporting.
  • doped polyazole films can be obtained by a process comprising the steps
  • step B) applying a layer using the mixture according to step A) on a support or on an electrode
  • step C) Heating of the flat structure / layer obtainable according to step B) under inert gas to temperatures of up to 350 ° C, preferably up to 280 ° C with the formation of the polyazole polymer.
  • step D) Treatment of the membrane formed in step C) (until it is self-supporting).
  • step A The aromatic or heteroaromatic carboxylic acid and tetraamino compounds to be used in step A) have been described above.
  • the polyphosphoric acid used in step A) is commercially available polyphosphoric acids such as are available, for example, from Riedel-de Haen.
  • the polyphosphoric acids H n + 2 P n ⁇ 3n + ⁇ (n> 1) usually have a content calculated as P 2 0 5 (acidimetric) of at least 83%.
  • a dispersion / suspension can also be produced.
  • the mixture produced in step A) has a weight ratio of polyphosphoric acid to the sum of all monomers of 1: 10000 to 10000: 1, preferably 1: 1000 to 1000: 1, in particular 1: 100 to 100: 1.
  • step B) takes place by means of measures known per se (casting, spraying, knife coating) which are known from the prior art for polymer film production. All carriers which are inert under the conditions are suitable as carriers.
  • phosphoric acid Concentrated phosphoric acid, 85%
  • the viscosity can be adjusted to the desired value and the formation of the membrane can be facilitated.
  • the layer produced according to step B) has a thickness between 20 and 4000 ⁇ m, preferably between 30 and 3500 ⁇ m, in particular between 50 and 3000 ⁇ m.
  • step A) also contains tricarboxylic acids or tetracarboxylic acids, this results in branching / crosslinking of the polymer formed. This contributes to the improvement of the mechanical property.
  • the inert gases to be used in step C) are known in the art. These include in particular nitrogen and noble gases such as neon, argon, helium.
  • the formation of oligomers and / or polymers can already be brought about by heating the mixture from step A) to temperatures of up to 350 ° C., preferably up to 280 ° C. Depending on the selected temperature and duration, the heating in step C) can then be partially or completely dispensed with.
  • This variant is also the subject of the present invention.
  • the treatment of the membrane in step D) takes place at temperatures above 0 ° C. and below 150 ° C., preferably at temperatures between 10 ° C. and 120 ° C., in particular between room temperature (20 ° C.) and 90 ° C., in the presence of Moisture or water and / or water vapor or and / or water-containing phosphoric acid of up to 85%.
  • the treatment is preferably carried out under normal pressure, but can also be carried out under the action of pressure. It is essential that the treatment takes place in the presence of sufficient moisture, as a result of which the polyphosphoric acid present contributes to the solidification of the membrane by partial hydrolysis with the formation of low molecular weight polyphosphoric acid and / or phosphoric acid.
  • the partial hydrolysis of the polyphosphoric acid in step D) leads to a solidification of the membrane and to a decrease in the layer thickness and formation of a membrane with a thickness between 15 and 3000 ⁇ m, preferably between 20 and 2000 ⁇ m, in particular between 20 and 1500 ⁇ m, which is self-supporting is.
  • the intra- and intermolecular structures (interpenetrating networks IPN) present in the polyphosphoric acid layer according to step B) lead in step C) to an orderly membrane formation, which is responsible for the special properties of the membrane formed.
  • the upper temperature limit of the treatment in step D) is generally 150 ° C. With extremely short exposure to moisture, for example superheated steam, this steam can also be hotter than 150 ° C. The duration of the treatment is essential for the upper temperature limit.
  • the partial hydrolysis (step D) can also take place in climatic chambers in which the hydrolysis can be specifically controlled under the influence of moisture.
  • the humidity can be specifically adjusted by the temperature or saturation of the contacting environment, for example gases such as air, nitrogen, carbon dioxide or other suitable gases, or water vapor.
  • gases such as air, nitrogen, carbon dioxide or other suitable gases, or water vapor.
  • the duration of treatment depends on the parameters selected above.
  • the treatment time depends on the thickness of the membrane.
  • the duration of treatment is between a few seconds to minutes, for example under the action of superheated steam, or until to whole days, for example in the air at room temperature and low relative humidity.
  • the treatment time is preferably between 10 seconds and 300 hours, in particular 1 minute to 200 hours.
  • the treatment time is between 1 and 200 hours.
  • the membrane obtained in step D) can be self-supporting, i.e. it can be detached from the carrier without damage and then processed directly if necessary.
  • the concentration of phosphoric acid and thus the conductivity of the polymer membrane can be adjusted.
  • the concentration of phosphoric acid is reported as moles of acid per mole of repeat unit of the polymer.
  • the process comprising steps A) to D) enables membranes with a particularly high phosphoric acid concentration to be obtained.
  • concentrations mol of phosphoric acid based on a repeating unit of the formula (I), for example polybenzimidazole
  • Such high levels of doping (concentrations) are only very high by doping polyazoles with commercially available orthophosphoric acid difficult or not accessible at all.
  • the membrane can still be crosslinked by the action of heat in the presence of atmospheric oxygen on the surface. This hardening of the membrane surface additionally improves the properties of the membrane.
  • Another method is radiation with ⁇ -rays. The radiation dose is between 5 and 200 kGy. According to a modification of the method described in which doped polyazole foils are produced by using polyphosphoric acid, these foils can also be produced by a method comprising the steps
  • step 3 heating the solution obtainable according to step 2) under inert gas to temperatures of up to 300 ° C, preferably up to 280 ° C to form the dissolved polyazole polymer.
  • step 5 Treatment of the membrane formed in step 4) until it is self-supporting.
  • the polyazole film can be provided with a plasma-polymerized ion-conducting layer before or after the doping with acid.
  • the plasma polymerization is preferably carried out after the doping.
  • the polyazole film can be provided with a layer according to the invention, which is a plasma-polymerized ion-conducting electrolyte membrane.
  • This layer prevents washing out of acid, so that this layer can also be referred to as a barrier layer. It has been shown that it is advantageous if the barrier layer is on the cathode side of the polymer electrolyte membrane, since the overvoltage is significantly reduced.
  • both sides of the polyazole film can also be provided with a layer according to the invention.
  • a layer according to the invention This results in a sandwich-like structure, the polyazole film, which may optionally be doped with acid, forming the middle layer, while the layers obtainable by the plasma process according to the invention are on the outside.
  • the term plasma describes a partially ionized gas.
  • a plasma can be generated by exciting a gas with electromagnetic radiation. The irradiation can take place both continuously and pulsed. Furthermore, DC or AC voltage sources can be used to generate the plasma. Devices for generating plasma can be obtained commercially, for example, from GaLa Gabler Labor Instrumente GmbH.
  • the plasma polymerization can be carried out at a pressure of 0.001 to 1000 Pa, preferably 0.1 to 100 Pa and particularly preferably 1 to 50 Pa.
  • the temperature during the plasma coating is preferably in the range from 0 ° to 300 °, preferably 5 to 250 ° C, without this being intended to impose any restriction.
  • the precursors to be used for plasma coating comprise a matrix-forming component.
  • the matrix-forming component in particular comprises unsaturated organic compounds. These include under other alkenes, especially ethylene, propylene, 1-hexene, 1-heptene, vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methylpentene-1; Alkynes, especially ethyne, propyne, butyne, hexyne-1; Vinyl compounds comprising an acidic group, especially vinylphosphonic acid, vinylsulfonic acid, acrylic acid and methacrylic acid; Vinyl compounds which comprise a basic group, in particular vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, N-vinylpyrrolidone, 2-vinylpyrrolidone, N -Vinylpyrrolidine
  • the aforementioned compounds can be used individually or as a mixture.
  • the proportion of matrix-forming component is generally 1 to 99% by weight, preferably 50 to 99% by weight, particularly preferably 60 to 99% by weight, based on the gas mixture used for the plasma coating.
  • the proportion of water is generally 1 to 99% by weight, preferably 1 to 50% by weight, particularly preferably 1 to 40% by weight, based on the gas mixture used for the plasma coating.
  • the gas mixture can comprise an inert carrier gas.
  • gases include, for example, noble gases such as helium and neon.
  • the components of the gas mixture used for plasma polymerization can be mixed before being introduced into the coating chamber. Furthermore, the different connections can also be introduced separately into the chamber.
  • the treatment time can be in a wide range.
  • the polyazole film, which can optionally be doped, is preferably coated for 10 seconds to 10 hours, preferably 1 minute to 1 hour, under plasma conditions.
  • the flow velocities of the gases in the vacuum chamber, the energy used to generate the plasma and further process parameters can be in a wide range, and the parameters customary for the method used can be selected. This information can generally be found in the operating instructions for the respective systems.
  • the preferred methods for producing a coating according to the invention include, in addition to plasma polymerization with continuous power feed, also the plasma pulse chemical vapor deposition method (PICVD).
  • PICVD plasma pulse chemical vapor deposition method
  • the PICVD method is described, for example, in Journal of the ceramic society of Japan, 99 (10), 894-902 (1991), the coating of curved surfaces also being disclosed (cf. WO 95/26427).
  • the electromagnetic radiation that excites the plasma is usually supplied in a pulsed manner with a continuous flow of the coating gases, with a thin layer (typically about 1 nm, monolayer range) being deposited on the substrate with each pulse.
  • a pulse pause After each power pulse there is a pulse pause, so that high coating speeds are possible without significant temperature stress on the substrate.
  • the height and duration of the power pulses and the duration of the pulse pause are particularly important for the production of a layer.
  • the pulse height is a performance measure in a PICVD process. It corresponds to the pulse power, i.e. H. the product of generator voltage and generator current during the pulse duration.
  • the proportion of the power that is actually injected into the plasma depends on a number of parameters, e.g. B. from the dimensioning of the pulse-emitting component and the reactor.
  • pulse duration 0.01 to 10 milliseconds, in particular 0.1 and 2 milliseconds
  • Pulse pause 1 to 1000 milliseconds, in particular 5 to 500 milliseconds
  • pulse height 10 to 100,000 watts.
  • the PICVD process is carried out with alternating voltage pulses with a frequency between 50 kHz and 300 gigahertz, the frequencies of 13.56 MHz and 2.45 GHz being particularly preferred.
  • the flow rate of the gas in the PICVD process is generally chosen so that the gas can be regarded as stationary during the pulse. Accordingly, the mass flows are generally in the range from 1 to 200 standard cm 3 / minute, preferably in the range from 5 to 100 standard cm 3 / minute.
  • the intrinsic conductivity of the plasma-polymerized ion-conducting layer is between 0.001 S / cm and 0.3 S / cm at 80 ° C., depending on the mixing ratio of the matrix-forming component and the water in the plasma, without any intention that this should impose a restriction. These values are determined in a simple manner by means of impedance spectroscopy, the plasma-polymerized layers being deposited on a dielectric support on which two or four electrodes, preferably platinum or gold electrodes, are deposited beforehand, depending on the measurement technique, using thin-film technology.
  • a Temperature-dependent measurement of the conductivity is carried out by heating the sample, for example by means of a heating plate with temperature regulation via a temperature sensor, which is positioned in the immediate vicinity of the layer to be measured, or by heating the sample in a suitable measuring cell in an oven.
  • the plasma-polymerized ion-conducting layers are characterized by high stability. Aging and stability studies can e.g. by an annealing in the temperature range between 100 ° C and 500 ° C, with a structural examination of the structure of the plasma-polymerized layers, e.g. Using infrared spectroscopy, statements about the structural changes occurring as a result of the tempering and thus about the stability of these layers are permitted.
  • the polyazole membranes provided with a layer obtainable by plasma polymerization show a surprisingly high conductivity over a wide temperature range.
  • the membranes obtainable according to the invention show a surprisingly high conductivity both at low temperatures in the range from 0 ° C. to 50 ° C. and at high temperatures above 120 ° C.
  • the polyazole membranes provided with a layer obtainable by plasma polymerization and doped with an acid have a high conductivity of at least 0.005, in particular at least 0.01 S / cm, particularly preferably at least 0.02S / cm at 120 ° C. without any limitation. These values are determined using impedance spectroscopy.
  • the specific conductivity can be measured by means of impedance spectroscopy in a 4-pole arrangement in potentiostatic mode and using platinum electrodes (wire, 0.25 mm diameter). The distance between the current-consuming electrodes is 2 cm.
  • the spectrum obtained is with a simple model consisting of a parallel arrangement view of an ohmic resistance and a capacitor evaluated.
  • the sample cross section of the phosphoric acid-doped membrane is immediately before the sample assembly measured. To measure the temperature dependence, the measuring cell is brought to the desired temperature in an oven and controlled via a Pt-100 thermocouple positioned in the immediate vicinity of the sample. After reaching the temperature, the sample is kept at this temperature for 10 minutes before starting the measurement.
  • the acid present in the polyazole film is surprisingly retained in the film by the coating according to the invention, without the acid being washed out during operation at low temperatures.
  • the procedure can be as follows:
  • the barrier effect is measured in a simple manner by changing the pH of water as a function of time.
  • a measuring cell which consists of two chambers, which are separated by a plasma-polymerized layer according to the invention.
  • the water to be measured and a pH electrode are located in one chamber, while in the other a solution, preferably a phosphoric acid solution of known concentration or a phosphoric acid-doped polyazole membrane is placed in direct contact with the plasma-polymerized layer.
  • the plasma-polymerized layer according to the invention is advantageously placed on a porous support, e.g. a porous film or porous ceramic.
  • a porous support e.g. a porous film or porous ceramic.
  • This coated carrier is inserted into a suitable holder, which separates the two chambers of the measuring cell and leaves a defined surface area of the plasma-polymerized layer on the carrier accessible on both sides.
  • a polyazole membrane coated according to the invention and doped with an acid shows a very low overvoltage. This property is maintained over a long period of operation and many start-up cycles.
  • the polyazole membranes provided with a coating according to the invention have a surprisingly high durability, which is evident both in operation at low and at high temperatures.
  • the present invention also relates to a membrane-electrode unit which has at least one polymer membrane according to the invention based on polyazoles.
  • a catalytically active layer can be applied to the membrane according to the invention and this can be connected to a gas diffusion layer.
  • the present invention also relates to a membrane-electrode unit which contains at least one polymer membrane according to the invention, optionally in combination with a further polymer membrane based on polyazoles or a polymer blend membrane.
  • MEAs that include polyazole membranes allow the fuel cell to operate at temperatures above 120 ° C. This applies to gaseous and liquid fuels, e.g. Gases containing hydrogen, e.g. be produced from hydrocarbons in an upstream reforming step. As an oxidant, e.g. Oxygen or air can be used.
  • gaseous and liquid fuels e.g. Gases containing hydrogen, e.g. be produced from hydrocarbons in an upstream reforming step.
  • an oxidant e.g. Oxygen or air can be used.
  • MEAs comprising polyazole membranes
  • they when operated above 120 ° C., they also work with pure platinum catalysts, ie without one another alloy component, have a high tolerance to carbon monoxide.
  • temperatures of 160 ° C for example, more than 1% CO can be contained in the fuel gas without this leading to a noticeable reduction in the performance of the fuel cell.
  • the MEAs with doped polyazole films can be operated in fuel cells without the fuel gases and oxidants not having to be humidified despite the possible high operating temperatures.
  • the fuel cell still works stably and the membrane does not lose its conductivity. This simplifies the entire fuel cell system and brings additional cost savings, since the management of the water cycle is simplified. This also improves the behavior of the fuel cell system at temperatures below 0 ° C.
  • the MEAs which have a doped polyazole film, surprisingly allow the fuel cell to be cooled to room temperature and below without any problems and then to be put back into operation without losing performance.
  • conventional fuel cells based on phosphoric acid must always be kept at a temperature above 80 ° C. even when the fuel cell system is switched off in order to avoid irreversible damage.
  • the MEAs with a polyazole membrane show very high long-term stability. It has been found that a fuel cell according to the invention may e.g. more than 1000 hours, preferably more than 2000 hours and particularly preferably more than 5000 hours at temperatures of more than 120 ° C. can be operated continuously with dry reaction gases without a noticeable degradation in performance being ascertainable. The power densities that can be achieved are very high even after such a long time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Sustainable Development (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Fuel Cell (AREA)
  • Physical Vapour Deposition (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production de membranes électrolytes en polymère par dépôt en phase gazeuse assisté par plasma. Ce procédé simplifie grandement l'état de la technique par le choix des matières de départ, des composés carbone ou fluoro-carbone et de l'eau. L'invention concerne également une membrane de polyazol revêtue au plasma.
PCT/EP2002/007734 2001-07-11 2002-07-11 Procede de production d'une membrane electrolyte en polymere polymerisee par plasma et membrane de polyazol revetue de plasma WO2003007411A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2003513069A JP2005520001A (ja) 2001-07-11 2002-07-11 プラズマ重合ポリマー電解質膜の製造方法及びプラズマ重合により被覆されたポリアゾール膜
US10/482,354 US20040186189A1 (en) 2001-07-11 2002-07-11 Method for producing a plasma-polymerized polymer electrolyte membrane and a polyazol membrane coated by plasma-polymerization
AU2002328339A AU2002328339A1 (en) 2001-07-11 2002-07-11 Method for producing a plasma-polymerized polymer electrolyte membrane and a polyazol membrane coated by plasma-polymerization
CA002448447A CA2448447A1 (fr) 2001-07-11 2002-07-11 Procede de production d'une membrane electrolyte en polymere polymerisee par plasma et membrane de polyazol revetue de plasma
EP02762348A EP1497882A2 (fr) 2001-07-11 2002-07-11 Procede de production d'une membrane electrolyte en polymere polymerisee par plasma et membrane de polyazol revetue de plasma
KR10-2003-7016749A KR20040014572A (ko) 2001-07-11 2002-07-11 플라즈마 중합된 중합체 전해질 막의 제조방법 및플라즈마 중합에 의해 코팅된 폴리아졸막

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10133738A DE10133738A1 (de) 2001-07-11 2001-07-11 Verfahren zur Herstellung einer plasmapolymerisierten Polymer-Elektrolytmembran
DE10133738.8 2001-07-11

Publications (2)

Publication Number Publication Date
WO2003007411A2 true WO2003007411A2 (fr) 2003-01-23
WO2003007411A3 WO2003007411A3 (fr) 2004-11-04

Family

ID=7691424

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/007734 WO2003007411A2 (fr) 2001-07-11 2002-07-11 Procede de production d'une membrane electrolyte en polymere polymerisee par plasma et membrane de polyazol revetue de plasma

Country Status (8)

Country Link
EP (1) EP1497882A2 (fr)
JP (1) JP2005520001A (fr)
KR (1) KR20040014572A (fr)
CN (1) CN1610984A (fr)
AU (1) AU2002328339A1 (fr)
CA (1) CA2448447A1 (fr)
DE (1) DE10133738A1 (fr)
WO (1) WO2003007411A2 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004024796A1 (fr) * 2002-08-29 2004-03-25 Pemeas Gmbh Procede pour produire des membranes polymeres conductrices de protons, membranes polymeres perfectionnees et leur utilisation dans des piles a combustible
WO2004030135A2 (fr) * 2002-09-13 2004-04-08 Pemeas Gmbh Membrane conductrice de protons et son utilisation
WO2004034498A3 (fr) * 2002-10-04 2005-05-12 Pemeas Gmbh Membrane polymere conductrice de protons recouverte d'une couche catalytique et contenant des polyazoles, et son utilisation dans des piles a combustible
US7332530B2 (en) 2002-08-02 2008-02-19 Celanese Ventures Gmbh Proton-conducting polymer membrane comprising a polymer with sulphonic acid groups and use thereof in fuel cells
US7445864B2 (en) 2002-07-06 2008-11-04 Basf Fuel Cell Gmbh Functionalized polyazoles, method for the production thereof, and use thereof
US7625652B2 (en) 2002-04-25 2009-12-01 Basf Fuel Cell Gmbh Multilayer electrolyte membrane
US7736778B2 (en) 2002-10-04 2010-06-15 Basf Fuel Cell Gmbh Proton conducting polymer membrane comprising phosphonic acid groups containing polyazoles and the use thereof in fuel cells
US7745030B2 (en) 2002-10-04 2010-06-29 Basf Fuel Cell Gmbh Proton-conducting polymer membrane comprising sulfonic acid-containing polyazoles, and use thereof in fuel cells
US7795372B2 (en) 2002-08-29 2010-09-14 Basf Fuel Cell Gmbh Polymer film based on polyazoles, and uses thereof
US7820314B2 (en) 2003-07-27 2010-10-26 Basf Fuel Cell Research Gmbh Proton-conducting membrane and use thereof
US7846982B2 (en) 2002-03-06 2010-12-07 Pemeas Gmbh Proton conducting electrolyte membrane having reduced methanol permeability and the use thereof in fuel cells
US7846983B2 (en) 2002-03-05 2010-12-07 Basf Fuel Cell Gmbh Proton conducting electrolyte membrane for use in high temperatures and the use thereof in fuel cells
US8652704B2 (en) 2004-06-30 2014-02-18 Tdk Corporation Direct alcohol fuel cell with cathode catalyst layer containing silver and method for producing the same

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100727216B1 (ko) * 2004-11-19 2007-06-13 주식회사 엘지화학 신규한 술폰화 공중합체 및 이를 이용한 전해질막
KR100706067B1 (ko) * 2005-01-25 2007-04-11 한양대학교 산학협력단 산 또는 염기 도핑된 미세다공성을 갖는 수소이온 전도성 고분자, 그 제조방법, 상기 고분자를 이용한 고분자막, 및 그 고분자막을 채용한 연료전지
DE102006040749A1 (de) * 2006-08-31 2008-03-06 Daimler Ag Oxidationsstabilisierte Polymer-Elektrolyt-Membranen für Brennstoffzellen
FR2908558B1 (fr) * 2006-11-13 2008-12-19 Commissariat Energie Atomique Materiau d'electrolyte silicie pour pile a combustible, procede pour sa realisation et pile a combustible mettant en oeuvre un tel materiau.
FR2928227B1 (fr) * 2008-02-29 2010-04-02 Commissariat Energie Atomique Procede de fabrication d'une membrane polymerique a conduction ionique pour pile a combustible.
JP2012049118A (ja) * 2010-07-28 2012-03-08 Sumitomo Chemical Co Ltd 高分子電解質、高分子電解質膜およびポリアリーレン系化合物
JP2012046741A (ja) * 2010-07-28 2012-03-08 Sumitomo Chemical Co Ltd 高分子電解質組成物、高分子電解質および含硫黄複素環芳香族化合物
WO2017217628A1 (fr) * 2016-06-14 2017-12-21 충남대학교산학협력단 Procédé de fabrication de couche mince de polymère-nanoparticules métalliques
CN111621208B (zh) * 2020-05-18 2021-11-05 江苏菲沃泰纳米科技股份有限公司 防水膜层及其制备方法、应用和产品

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032440A (en) * 1975-11-18 1977-06-28 The United States Of America As Represented By The Secretary Of The Interior Semipermeable membrane
EP0593011A1 (fr) * 1992-10-13 1994-04-20 Deutsche Carbone AG Procédé de préparation d'une membrane plasmatique composite et son utilisation
EP1020489A1 (fr) * 1999-01-15 2000-07-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Membrane d'electrolyte polymère notammant pour piles à combustible à méthanol et leur procédé de production
DE19914571A1 (de) * 1999-03-31 2001-01-04 Joerg Mueller Polymer-Elektrolyt-Membran mit integrierter plasmapolymerisierter ionenleitender Sperrschicht

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4806246A (en) * 1986-04-11 1989-02-21 Applied Membrane Technology, Inc. Pore size control using plasma polymerization techniques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032440A (en) * 1975-11-18 1977-06-28 The United States Of America As Represented By The Secretary Of The Interior Semipermeable membrane
EP0593011A1 (fr) * 1992-10-13 1994-04-20 Deutsche Carbone AG Procédé de préparation d'une membrane plasmatique composite et son utilisation
EP1020489A1 (fr) * 1999-01-15 2000-07-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Membrane d'electrolyte polymère notammant pour piles à combustible à méthanol et leur procédé de production
DE19914571A1 (de) * 1999-03-31 2001-01-04 Joerg Mueller Polymer-Elektrolyt-Membran mit integrierter plasmapolymerisierter ionenleitender Sperrschicht

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YASUDA H ET AL: "ULTRATHIN COATING BY PLASMA POLYMERIZATION APPLIED TO CORNEAL CONTACT LENS" COMPENDEX, November 1975 (1975-11), XP002225081 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7846983B2 (en) 2002-03-05 2010-12-07 Basf Fuel Cell Gmbh Proton conducting electrolyte membrane for use in high temperatures and the use thereof in fuel cells
US7846982B2 (en) 2002-03-06 2010-12-07 Pemeas Gmbh Proton conducting electrolyte membrane having reduced methanol permeability and the use thereof in fuel cells
US7625652B2 (en) 2002-04-25 2009-12-01 Basf Fuel Cell Gmbh Multilayer electrolyte membrane
US7445864B2 (en) 2002-07-06 2008-11-04 Basf Fuel Cell Gmbh Functionalized polyazoles, method for the production thereof, and use thereof
US7332530B2 (en) 2002-08-02 2008-02-19 Celanese Ventures Gmbh Proton-conducting polymer membrane comprising a polymer with sulphonic acid groups and use thereof in fuel cells
WO2004024796A1 (fr) * 2002-08-29 2004-03-25 Pemeas Gmbh Procede pour produire des membranes polymeres conductrices de protons, membranes polymeres perfectionnees et leur utilisation dans des piles a combustible
US7883818B2 (en) 2002-08-29 2011-02-08 Basf Fuel Cell Gmbh Process for producing proton-conducting polymer membranes, improved polymer membranes and the use thereof in fuel cells
US7795372B2 (en) 2002-08-29 2010-09-14 Basf Fuel Cell Gmbh Polymer film based on polyazoles, and uses thereof
WO2004030135A3 (fr) * 2002-09-13 2005-05-12 Pemeas Gmbh Membrane conductrice de protons et son utilisation
US8716356B2 (en) 2002-09-13 2014-05-06 Basf Fuel Cell Gmbh Proton-conducting membrane and its use
US8277983B2 (en) 2002-09-13 2012-10-02 Basf Fuel Cell Gmbh Proton-conducting membrane and its use
WO2004030135A2 (fr) * 2002-09-13 2004-04-08 Pemeas Gmbh Membrane conductrice de protons et son utilisation
US7736778B2 (en) 2002-10-04 2010-06-15 Basf Fuel Cell Gmbh Proton conducting polymer membrane comprising phosphonic acid groups containing polyazoles and the use thereof in fuel cells
US7745030B2 (en) 2002-10-04 2010-06-29 Basf Fuel Cell Gmbh Proton-conducting polymer membrane comprising sulfonic acid-containing polyazoles, and use thereof in fuel cells
US7661542B2 (en) 2002-10-04 2010-02-16 Basf Fuel Cell Gmbh Proton-conducting polymer membrane that contains polyazoles and is coated with a catalyst layer, and application therof in fuel cells
WO2004034498A3 (fr) * 2002-10-04 2005-05-12 Pemeas Gmbh Membrane polymere conductrice de protons recouverte d'une couche catalytique et contenant des polyazoles, et son utilisation dans des piles a combustible
US7820314B2 (en) 2003-07-27 2010-10-26 Basf Fuel Cell Research Gmbh Proton-conducting membrane and use thereof
US8323810B2 (en) 2003-07-27 2012-12-04 Basf Fuel Cell Research Gmbh Proton-conducting membrane and use thereof
US8652704B2 (en) 2004-06-30 2014-02-18 Tdk Corporation Direct alcohol fuel cell with cathode catalyst layer containing silver and method for producing the same

Also Published As

Publication number Publication date
CN1610984A (zh) 2005-04-27
CA2448447A1 (fr) 2003-01-23
DE10133738A1 (de) 2003-02-06
KR20040014572A (ko) 2004-02-14
EP1497882A2 (fr) 2005-01-19
JP2005520001A (ja) 2005-07-07
AU2002328339A1 (en) 2003-01-29
WO2003007411A3 (fr) 2004-11-04

Similar Documents

Publication Publication Date Title
EP2267059B1 (fr) Membrane conducteur de protons et son application
EP1518282B1 (fr) Membrane electrolyte multicouche
EP1379572B1 (fr) Membrane conductrice de protons et son utilisation
EP1550174B1 (fr) Membrane conductrice de protons et son utilisation
EP1497882A2 (fr) Procede de production d'une membrane electrolyte en polymere polymerisee par plasma et membrane de polyazol revetue de plasma
EP1527490B1 (fr) Unite membrane-electrode a couche de polyimide
EP1719200B1 (fr) Unité membrane-électrodes à puissance élevée et son utilisation dans des piles a combustible
EP1559162B1 (fr) Membrane polymere conductrice de protons recouverte d'une couche catalytique et contenant des polyazoles, et son utilisation dans des piles a combustible
DE10239701A1 (de) Polymerfolie auf Basis von Polyazolen und deren Verwendung
EP1652259A2 (fr) Membrane a conduction de protons et utilisation correspondante
EP1583789A1 (fr) Polyazoles a haut poids moleculaire
EP1701995B1 (fr) Membrane conductrice de protons et son utilisation
US20040186189A1 (en) Method for producing a plasma-polymerized polymer electrolyte membrane and a polyazol membrane coated by plasma-polymerization
EP1537164A1 (fr) Procede pour produire des membranes polymeres conductrices de protons, membranes polymeres perfectionnees et leur utilisation dans des piles a combustible
EP2373406A1 (fr) Procédé de fabrication d'une membrane conduisant les protons
DE10330461A1 (de) Verfahren zur Herstellung von protonenleitenden Polymermembranen, verbesserte Polymermembranen und deren Anwendung in Brennstoffzellen
DE102012007178A1 (de) Verbesserte Membran-Elektrodeneinheiten und Brennstoffzellen mit langer Lebensdauer
WO2012153172A1 (fr) Polyazoles stabilisés mécaniquement, contenant au moins un alcool polyvinylique

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AU BR CA CN IL JP KR MX US

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR US

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2002762348

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2448447

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 028121287

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 1020037016749

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 10482354

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2003513069

Country of ref document: JP

WWP Wipo information: published in national office

Ref document number: 2002762348

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 2002762348

Country of ref document: EP