Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0081—After-treatment of organic or inorganic membranes
  • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0081—After-treatment of organic or inorganic membranes
  • B01D67/0095—Drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
  • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/18—Polybenzimidazoles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/22—Polybenzoxazoles
• • 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
  • H01M8/1041—Polymer electrolyte composites, mixtures or blends
  • H01M8/1046—Mixtures of at least one polymer and at least one additive
  • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
• • 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 present invention relates to an acid-doped polymer membrane based on polyazoles, a process for producing it and its use.
• the acid-doped polymer membrane of the invention can be used in a variety of applications because of its excellent chemical, thermal and mechanical properties and is particularly useful as polymer electrolyte membrane (PEM) in PEM fuel cells.
• PEM polymer electrolyte membrane
• Acid-doped polyazole membranes for use in PEM fuel cells are already known.
• the basic polyazole membranes are doped with concentrated phosphoric acid or sulfuric acid and act as proton conductors and separators in polymer electrolyte membrane fuel cells (PEM fuel cells).
• such polymer electrolyte membranes can, when processed to produce a membrane-electrode unit (MEE), be used in fuel cells at continuous operating temperatures above 100° C., in particular above 120° C.
• MEE membrane-electrode unit
• This high continuous operating temperature allows the activity of the catalysts based on noble metals present in the membrane-electrode unit (MEE) to be increased.
• significant amounts of carbon monoxide are present in the reformer gas and these usually have to be removed by costly gas treatment or gas purification procedures.
• the opportunity of increasing the operating temperature enables significantly higher concentrations of CO impurities to be tolerated over the long term.
• the acid-doped, polyazole-based polymer membranes known hitherto display a favorable property profile. However, owing to the applications sought for PEM fuel cells, in particular in automobile and stationary applications, they still require overall improvement. Furthermore, the polymer membranes known hitherto have a high content of dimethylacetamide (DMAc) which cannot be removed completely by known drying methods.
• DMAc dimethylacetamide
• the polyazole-based polymer membranes known hitherto still display mechanical properties which are unsatisfactory for the above application after they have been doped with acid. This mechanical instability is reflected in a low modulus of elasticity, a low ultimate tensile strength and a low fracture toughness.
• the present invention provides a doped polymer membrane based on polyazoles, obtainable by a process comprising the steps
• step A) drying the film formed in step A) until it is self-supporting
• step B) treating the film obtained in step B) with a treatment liquid at a temperature in the range from room temperature to the boiling point of the treatment liquid,
• step D) doping the film treated according to step D) with a doping agent.
• EP-A-0816415 describes a method of dissolving polymers based on polyazoles using N,N-dimethylacetamide as polar, aprotic solvent at temperatures above 260° C.
• a substantially more gentle process for preparing solutions based on polyazoles is disclosed in the German patent application 10052237.8.
• polymers based on polyazoles preference is given to polymers comprising recurring azole units of the formula (I) and/or (II)
• Ar are identical or different and are each a tetravalent aromatic or heteroaromatic group which may have one or more rings,
• Ar 1 are identical or different and are each a divalent aromatic or heteroaromatic group which may have one or more rings,
• Ar 2 are identical or different and are each a trivalent aromatic or heteroaromatic group which may have one or more rings,
• X are identical or different and are each oxygen, sulfur or an amino group which bears a hydrogen atom and a group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as other radical.
• Preferred aromatic or heteroaromatic groups are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenyl sulfone, quinoline, pyridine, bipyridine, anthracene and phenanthrene, all of which may also be substituted.
• Ar 1 can have any substitution pattern; in the case of phenylene, for example, Ar 1 can be ortho-, meta-or para-phenylene. Particularly preferred groups are derived from benzene and biphenylene, each of which may also be substituted.
• Preferred alkyl groups are short-chain alkyl groups having from 1 to 4 carbon atoms, e.g. methyl, ethyl, n-propyl or isopropyl and tert-butyl groups.
• Preferred aromatic groups are phenyl or naphthyl groups.
• the alkyl groups and the aromatic groups may be substituted.
• Preferred substituents are halogen atoms such as fluorine, amino groups or short-chain alkyl groups such as methyl or ethyl groups.
• the polyazoles used according to the invention can in principle also have different recurring units which differ, for example, in their radical X. However, they preferably have only identical radicals X in a recurring unit.
• the polymer comprising recurring azole units is a copolymer comprising at least two units of the formula (I) and/or (II) which differ from one another.
• the polymer comprising recurring azole units is a polyazole comprising only units of the formula (I) and/or (II).
• the number of recurring azole units in the polymer is preferably greater than or equal to 10.
• Particularly preferred polymers comprise at least one 100 recurring azole units.
• polymers comprising recurring benzimidazole units are preferably used.
• An example of an extremely advantageous polymer comprising recurring benzimidazole units is represented by the formula (III):
• n is an integer greater than or equal to 10, preferably greater than or equal to 100.
• step A Casting of a polymer film from a polymer solution according to step A) is carried out by means of measures known per se from the prior art.
• Drying of the film in step B) is carried out at temperatures in the range from room temperature to 300° C. Drying is carried out under atmospheric pressure or reduced pressure. The drying time depends on the thickness of the film and is preferably from 10 seconds to 24 hours.
• the film which has been dried in step B) is subsequently self-supporting and can be processed further. Drying is carried out by means of drying methods customary in the films industry.
• step B As a result of the drying procedure carried out in step B), the polar, aprotic organic solvent is very largely removed. Thus, the residual content of the polar, aprotic organic solvent is usually 10 - 23%.
• a further lowering of the residual solvent content to below 2% by weight can be achieved by increasing the drying temperature and drying time, but this significantly prolongs the subsequent doping of the film, for example with phosphoric acid.
• a residual solvent content of 5-15% is thus useful for reducing the doping time.
• the treatment of the film which has been dried in step B) uses a treatment liquid and is out in the temperature range from room temperature (20° C.) and the boiling point of the treatment liquid at atmospheric pressure.
• solvents which are liquid at room temperature [i.e. 20° C.] selected from the group consisting of alcohols, ketones, alkanes (aliphatic and cycloaliphatic), ethers (aliphatic and cycloaliphatic), esters, carboxylic acids, with the abovementioned group members being able to be halogenated, water, inorganic acids (e.g. H 3 PO 4 , H 2 SO 4 ) and mixtures thereof.
• solvents which are liquid at room temperature [i.e. 20° C.] selected from the group consisting of alcohols, ketones, alkanes (aliphatic and cycloaliphatic), ethers (aliphatic and cycloaliphatic), esters, carboxylic acids, with the abovementioned group members being able to be halogenated, water, inorganic acids (e.g. H 3 PO 4 , H 2 SO 4 ) and mixtures thereof.
• inorganic acids e.g. H 3 PO 4 , H
• C1-C10 alcohols C2-C5 ketones, C1-C10-alkanes (aliphatic and cycloaliphatic), C2-C6-ethers (aliphatic and cycloaliphatic), C2-C5 esters, C1-C3 carboxylic acids, dichloromethane, water, anorganic acids (e.g. H 3 PO 4 , H 2 SO 4 ) and mixtures thereof.
• anorganic acids e.g. H 3 PO 4 , H 2 SO 4
• the treatment liquid introduced in step C) can be removed by means of the drying procedure carried out in step D).
• the drying procedure depends on the partial vapor pressure of the treatment liquid chosen. Drying is usually carried out at atmospheric pressure and temperatures in the range from 20° C. to 200° C. More gentle drying can also be carried out under reduced pressure. In place of drying, the membrane can also be dabbed to free it of excess treatment liquid in step D). The order is not critical.
• step E) the doping of the film obtained from step C) or D) is carried out.
• the film is wetted with a doping agent or laid in this.
• doping agent for the polymer membrane of the invention use is made of acids, preferably all known Lewis and Br ⁇ nsted acids, in particular inorganic Lewis and Br ⁇ nsted acids.
• heteropolyacids are inorganic polyacids which have at least two different central atoms and are in each case partial mixed anhydrides formed from weak, polybasic oxo acids of a metal (preferably Cr, Mo, V, W) and a nonmetal (preferably As, I, P, Se, Si, Te). They include, inter alia, 12-molybdophosphoric acid and 12-tungstophosphoric acid.
• Doping agents which are particularly preferred for the purposes of the invention are sulfuric acid and phosphoric acid.
• a very particularly preferred doping agent is phosphoric acid (H 3 PO 4 ).
• the polymer membranes of the invention are doped.
• doped polymer membranes are polymer membranes which, owing to the presence of doping agents, display increased proton conductivity compared to the undoped polymer membranes.
• Processes for preparing doped polymer membranes are known. In a preferred embodiment of the present invention, they are obtained by wetting a film of the polymer concerned with concentrated acid, for example with highly concentrated phosphoric acid, for a suitable time, preferably 5 minutes -96 hours, particularly preferably 1 -72 hours, at temperatures in the range from room temperature to 100° C. and atmospheric or superatmospheric pressure.
• the conductivity of the polar membrane of the invention can be influenced via the degree of doping.
• the conductivity increases with increasing concentration of doping agent until a maximum value has been reached.
• the degree of doping is reported as mol of acid per mol of recurring units of the polymer.
• a degree of doping of from 3 to 15, in particular from 6 to 12, is preferred.
• the polymer membrane of the invention has improved materials properties compared to the previously known doped polymer membranes. In particular, they have very good mechanical properties and perform better than untreated membranes.
• the polymer membranes of the invention display improved proton conductivity compared to untreated membranes.
• the doped polymer membranes of the invention include, inter alia, use in fuel cells, in electrolysis, in capacitors and in battery systems. Owing to their property profile, the doped polymer membranes are preferably used in fuel cells.
• the present invention also relates to a membrane-electrode unit comprising at least one polymer membrane according to the invention.
• a membrane-electrode unit comprising at least one polymer membrane according to the invention.
• the disclosure in the abovementioned references [U.S. Pat. No. 4,191,618, U.S. Pat. No. 4,212,714 and U.S. Pat. No. 4,333,805] in respect of the structure and production of membrane-electrode units is incorporated by reference into the present description.
• the untreated films were laid in 85% strength H 3 PO 4 for 96 hours.
• H 2 O content and residual solvent content of the film are determined by Karl Fischer (KF) titration.
• the water content of the film is determined directly as follows by KF titration using a Mettler-Toledo apparatus.
• the sample which is present in a closed sample vial, is heated to 250° C. and dried at this temperature.
• the gas liberated in this way is passed directly into a closed titration vessel and analyzed by means of a Karl Fischer [KF] reagent.
• the residual solvent content is determined by determining the weight before and after drying.
• the films were boiled in water for 1 hour. The water bath was then changed and the films were boiled for a further hour. The films were subsequently rinsed with fresh water and finally dried at 160° C. for 3 hours. H 2 0 content and residual solvent content were determined on the treated films by KF titration. The membranes were obtained by doping the films in 85% strength H 3 PO 4 for 96 hours.
• the films were boiled in water for 1 hour. The water bath is then changed and the films are boiled for a further hour. The films were subsequently dabbed with a cloth and used further in moist form. H 2 O content and residual solvent content of the film were determined by KF titration. The membranes were doped in 85% strength H 3 PO 4 for 96 hours.
• the films were placed in methanol and boiled under reflux for 2 hours (beginning when the methanol started to boil). The films were taken out and dried firstly for 1 minute in air minute in air and then at 100C. under reduced pressure in a drying oven for 2 hours. H 2 O content and residual organic solvent content of the film were determined by KF titration. The membranes were doped in 85% strength H 3 PO 4 for 96 hours.
• the films were placed in acetone and boiled under reflux for 2 hours (beginning when the acetone started to boil). The films were then dried firstly for 1 minute in air at RT and subsequently at 100 20 C. under reduced pressure in a drying oven for 2 hours. H 2 O content and residual solvent content of the film were determined by KF titration. The membranes were doped in 85% strength H 3 PO 4 for 96 hours.
• FIG. 1 shows the result of the KF titration.
• the residual organic solvent is removed completely by washing with water.
• the residual organic solvent content is reduced from 16.6% to 3.7 or 2.3% by washing with acetone or with methanol, respectively.
• FIG. 2 shows a proton conductivity which is improved by 10% even at room temperature and is retained or improved further at elevated temperature.
• the specific conductivity is measured by means of impedance spectroscopy in a 4-pole arrangement in the potentiostatic mode using platinum electrodes (wire, 0.25 mm diameter). The distance between the current collector electrodes is 2 cm.
• the spectrum obtained is evaluated using a simple model consisting of a parallel arrangement of an ohmic resistance and a capacitor.
• the specimen cross section of the membrane doped with phosphoric acid is measured immediately before mounting of the specimen. To measure the temperature dependence, the measuring cell is brought to the desired temperature in an oven and the temperature is regulated via a Pt-100 temperature sensor positioned in the immediate proximity of the specimen. After reaching the temperature, the specimen is maintained at this temperature for 10 minutes before commencement of the measurement.
• An untreated membrane displays an elongation at break of 55% while a membrane according to the invention has an elongation at break in the range from 58% to 75%.

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• 2001
  • 2001-03-01 DE DE10109829A patent/DE10109829A1/de not_active Withdrawn
• 2002
  • 2002-03-01 CN CNB028057899A patent/CN100367552C/zh not_active Expired - Fee Related
  • 2002-03-01 WO PCT/EP2002/002216 patent/WO2002071518A1/de active Application Filing
  • 2002-03-01 CA CA002439541A patent/CA2439541A1/en not_active Abandoned
  • 2002-03-01 EP EP02748325A patent/EP1368845A1/de not_active Withdrawn
  • 2002-03-01 US US10/468,385 patent/US20040247974A1/en not_active Abandoned
  • 2002-03-01 JP JP2002570329A patent/JP4532828B2/ja not_active Expired - Fee Related
• 2007
  • 2007-10-31 US US11/931,734 patent/US20080280182A1/en not_active Abandoned
• 2010
  • 2010-03-09 US US12/720,026 patent/US8168105B2/en not_active Expired - Fee Related

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