WO2000077874A1 - Membranes polymeres conductrices de protons - Google Patents

Membranes polymeres conductrices de protons Download PDF

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Publication number
WO2000077874A1
WO2000077874A1 PCT/US2000/016006 US0016006W WO0077874A1 WO 2000077874 A1 WO2000077874 A1 WO 2000077874A1 US 0016006 W US0016006 W US 0016006W WO 0077874 A1 WO0077874 A1 WO 0077874A1
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oxyacid
methanol
polymer solution
proton conducting
membranes
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PCT/US2000/016006
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English (en)
Inventor
Harry R. Allcock
Michael A. Hofmann
Serguei N. Lvov
Xiang Y. Zhou
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The Penn State Research Foundation
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Priority to AU54803/00A priority Critical patent/AU5480300A/en
Publication of WO2000077874A1 publication Critical patent/WO2000077874A1/fr

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    • 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
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0018—Thermally induced processes [TIPS]
    • 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
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
    • 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
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • 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
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • 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
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. 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
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • 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
    • C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
    • C08J2385/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 generally relates to proton conducting polymer membranes and methods of manufacture thereof, which are useful in methanol-based fuel cells.
  • Proton conducting polymer membranes or polymer electrolyte membranes, are of general interest because such membranes can be used to conduct protons in fuel cells, which convert methanol into electrical energy and show promise as low emission power sources.
  • Methanol-based fuel cells produce power through the electrochemical reaction of methanol and oxygen whereby oxygen is reduced at the cathode and methanol is oxidized at the anode.
  • An appropriate polymer membrane is insoluble in water and methanol and is selectively permeable to hydrogen ions.
  • Fluorocarbon based resins such as NAFIONTM and its derivatives, are the most common materials used in the manufacture of solid-polymer electrolyte membranes in methanol fuel cells. The membranes are stable and conduct protons.
  • the membranes are permeable to methanol and allow significant amounts of methanol to diffuse through the membrane and crossover from the anode to cathode resulting in the spontaneous oxidation of methanol at the cathode. This oxidation depletes fuel from the cell and results in a loss of energy and efficiency.
  • NAFIONTM membranes are not cost efficient because NAFIONTM is an expensive starting material and the fabricated membranes become unusable upon dehydration at elevated temperatures.
  • the polymeric membranes are formed by (a) dissolving a polymer, preferably a polyphosphazene, in an organic solvent to form a polymer solution; (b) adding an oxyacid to the polymer solution; (c) optionally, adding water to the polymer solution, preferably in a molar ratio equivalent to the oxyacid; (d) optionally, concentrating the polymer solution; (e) casting the polymer solution on a casting surface, such as one formed of or coated with TEFLONTM; and (f) removing the organic solvent, such as by a controlled evaporation, so as to form the polymeric membrane.
  • a particularly useful application for these polymeric membranes is in fuel cells, such as those wherein methanol and oxygen are converted into electrical energy.
  • Figure 1 is a schematic of an electrochemical cell used in the Examples to measure proton conductivity of the polymeric membranes.
  • Figure 2 is a schematic of an apparatus used in the Examples to measure methanol crossover of the polymeric membranes.
  • Figure 3 is a graph showing vapor pressure (mm Hg) curves for water and methanol versus water as a function of temperature (°C). The dashed line represents an interpolation for a 10% methanol- water (v/v) solution.
  • Figure 4 is a graph showing methanol crossover (cm-Hg) versus time
  • FIG. 5 is a schematic of an apparatus used in the Examples to measure methanol diffusion.
  • Figure 6 is a graph of the gas chromatography calibration curve used in the Examples to determine methanol content in the diffusion analysis. Detailed Description of the Invention
  • proton conducting polymer membranes a/k/a polymer electrolyte membranes
  • These proton conducting membranes exhibit excellent proton conductivity (comparable to standard commercially available membranes) and yet have increased resistance to methanol diffusion.
  • the polymer membranes are formed by combining a polymer, an oxyacid (such as phosphorus oxyacid), and water.
  • polymeric membrane refers to proton conducting membranes.
  • the polymeric membrane preferably has a thickness between about 0.02 and about 0.03 cm.
  • the polymeric membranes exhibit, at room temperature (e.g., 20-25 °C) proton conductivities in the range of 10 "3 to 10 "2 S/cm, which is approximately equal to the proton conductivity of polymer electrolyte membranes standard in the fuel cell industry, such as NAFIONTM 117.
  • the polymeric membranes preferably are more resistant to methanol diffusion than NAFIONTM 117.
  • the polymeric membranes should exhibit, at room temperature, methanol crossover rates that are at least approximately 2- 5 times slower than those of NAFIONTM 117.
  • the polymeric membranes also should continue to exhibit these proton conducting and methanol crossover resistance properties even after weeks of exposure to water.
  • the polymer membranes are formed by combining a polymer, an oxyacid, and optionally and preferably water.
  • the polymer is a water insoluble organic polymer or a hybrid inorganic/ organic polymer.
  • the polymer can be polymerized and substituted using techniques known in the art.
  • the polymer preferably is mechanically flexible, rather than rigid or brittle.
  • the preferred polymer is a polyphosphazene.
  • Other representative polymers useful in the present polymeric membranes include polyalkenes, polyacrylics, polyvinyl ethers, polyvinylhalides, polystyrenes, polyesters, polyurethanes, and polyamides.
  • Polyphosphazene polymers may be substituted with one or more side group.
  • side groups include alkyl, fluoralkyl, alkoxy, fluoroalkoxy, alkylamino, aryl, aryloxy, and arylamino groups. Any aryl side group may be derivatized with one or more functionality, including, for example, halo, alkyl, fluoralkyl, alkoxy, fluoroalkoxy, alkylamino, and fluoroalkylamino functionalities.
  • Representative oxyacids suitable for use in the present polymeric membranes include boric, carbonic, cyanic, isocyanic, silicic, nitric, nitrous, phosphoric, phosphorous, hypophosphorous, arsenic, arsenious, antimonic, sulfuric, sulfurous, selenic, selenious, telluric, chromic, dichromic, perchloric, chloric, chlorous, hypochlorous, bromic, bromous, hypobromous, periodic, iodic, hypoiodous, permanganic, manganic, pertechnetic, technetic, perrhennic, rehnnic acids, and their condensation products, for example pyrophosphoric, triphosphoric, and polyphosphoric acid.
  • the acids may be derivatized with one or more of the following groups: alkyl, fluoroalkyl, alkoxy, flouroalkoxy, alkylamino, fluoroalkylamino, aryl, aryloxy, and arylamino groups. Any aryl may be derivatized with one or more functionality, including, for example, halo, alkyl, fluoroalkyl, alkoxy, fluoroalkyl, alkoxy, fluoroalkoxy, alkylamino, and fluoroalkylamino groups.
  • a preferred oxyacid is phosphorous oxychloride.
  • a preferred organic solvents include tetrahydrofuran (THF).
  • suitable solvents include dioxane, and N,N-dimethylformamide (DMF), as well as any solvent suitable for dissolving the polymer and miscible with the oxyacid and water.
  • the polymeric membranes are formed by (a) dissolving a polymer in an organic solvent to form a polymer solution, preferably at about 1 g polymer per 200 mL solvent;
  • a casting surface e.g., a TEFLONTM (polytetrafluoroethylene) coated glass slide or a TEFLONTM tray;
  • the cured polymeric membrane preferably is hydrolyzed and washed by soaking in distilled water and intermittently replacing the water with fresh distilled water until the pH of the water bath remains constant.
  • the hydrolyzed membrane then can, for example, be stored in water or incorporated, for example, into a methanol/oxygen fuel cell.
  • the polymeric membrane may be dehydrated and later refluxed with water to restore is conducting function.
  • the polymer solution concentration of step (d) can be conducted using techniques known in the art, such as by evaporation under vacuum or using a rotavapor.
  • step (f) typically must be conducted slowly, so as to avoid the formation of undesirable holes or bubbles in the membrane and the formation of a membrane which is not uniform overall.
  • the evaporation rate can be controlled using techniques known in the art, such as by nearly saturating the vapor space above the cast solution with the organic solvent.
  • the polymeric membranes described herein are useful in a variety of applications and devices requiring proton conducting polymer membranes.
  • a particularly useful application is in fuel cells, such as those wherein methanol and oxygen are converted into electrical energy.
  • the polymeric membranes also may have application in hydrogen/oxygen fuel cells.
  • the polymeric membranes may be used to increase fuel efficiency in such cells, for example, relative to NAFIONTM electrolyte membranes.
  • the polymeric membranes can be incorporated into devices for use processes for the separation of organic liquids from water.
  • Example 1 Preparation of a Proton Conducting Polyphosphazene Membrane Poly[bis(phenoxy)polyphosphazene] was synthesized according to standard methods, and then was isolated, purified, and dried. The polymer (1 g) was dissolved in 200 mL refluxing THF (VWR) over one hour. The solution was gravity filtered and then cooled to room temperature.
  • VWR refluxing THF
  • the apparatus depicted in Figure 1 was used to carry out the measurements of membrane conductivity.
  • the epoxy cell consists of two compartments containing 0.5 mol kg "1 hydrochloric acid that are separated by two VITONTM O-rings and the polymeric membrane to be measured. Two gaskets pressing on the membrane ensured no liquid connection between the compartments.
  • One platinum electrode was placed in each compartment.
  • R is the resistance of the membrane
  • h is the membrane thickness
  • the system developed for the methanol crossover measurements is shown in Figure 2.
  • the cylindrical, stainless steel cell was separated into two chambers by the sample polymer membrane supported by a stainless steel or TEFLONTM mesh to prevent deformation and cracking.
  • the upper chamber was filled with air or methanol solution while the lower chamber was evacuated using a vacuum pump.
  • Methanol crossover rate was determined by monitoring the pressure change in the vacuum chamber due to crossover of water and methanol penetrating into the chamber through the membrane.
  • the top surface of the membrane was exposed to air for approximately an hour to ensure constant pressure and a sealed vacuum chamber.
  • An aqueous methanol solution, 10% (v/v) was then pumped into the upper chamber at a constant flow rate, 1.5 ml min "1 .
  • Pressures in both chambers were measured using pressure transducers.
  • the desired temperature was maintained using a tape heater and a temperature controller.
  • a thermocouple was installed to monitor the operational temperature of the polymer membrane.
  • the starting pressure in the vacuum chamber should be lower than the vapor pressure of methanol and higher than that of water at the operational temperature to distinguish the methanol crossover from water crossover. Thus, water entering the vacuum chamber remained in the liquid phase resulting in negligible pressure increase.
  • the vapor pressure vs. temperature diagrams for methanol and water in Figure 3 were used to determine the starting pressure.
  • a 50 % methanol (by volume) aqueous solution was pumped into the lower compartment.
  • the upper compartment was filled with fixed amount of distilled water in order to maintain equal sample volumes.
  • the system was maintained at constant temperature, preferably 20
  • Methanol concentration of the samples was determined by gas chromatography.
  • the calibration curve in Figure 6 was obtained by plotting the ratio of the methanol peak area to the ethanol peak area versus methanol concentration using standards containing 1% (v/v) ethanol and varying amounts of methanol.
  • the unknown samples from the diffusion test were each spiked with 1% ethanol and analyzed in the gas chromatograph. The ratios of the methanol peak area to ethanol peak area of the diffusion samples were then substituted into the calibration equation to determine the methanol concentration.
  • C (sample) is the concentration of methanol created in the water sample due to diffusion; measured analytically by GC, mol/cm 3 ;
  • V is the volume of analyzed sample, cm 3 ;
  • D obtained at different t should be the same value.
  • an Acuflow Series high- pressure pump was used to regulate the flow rate of methanol. Pressure was measured in the chambers using pressure transducers from Omega Engineering Co., and temperature was maintained, if necessary, with an Omega CN9000A temperature controller.
  • the membrane resistance was measured using an EIS130 from Gamry Instruments in the ionic conductivity measurements.
  • the methanol concentrations in the methanol diffusion analysis was measured using a gas chromatograph. Results and Discussion
  • the membranes contained about 60% water by weight. This was determined by blotting the surfaces of a membrane that was stored in water with a paper towel. The membrane was weighed and then placed under vacuum for about 24 hours ( ⁇ 1mm Hg). The dry membrane was weighed again and the difference in weight was attributed to initial water weight.
  • the membranes were white in color, with dimensions slightly smaller than that of the TEFLONTM tray. Typically the outer 0.25 cm of the membranes were trimmed off with a pair of scissors. The membranes typically were 0.02 to 0.03 cm in thickness. The membranes were slightly elastic, not brittle, and will stretch significantly if pulled before breaking. Ionic Conductivity Measurements
  • the polyphosphazene membrane (0.02 cm Hg/minute) was 2-5 times more resistant to methanol permeation than the NAFIONTM membrane (0.05 cm Hg/minute).
  • the polyphosphazene membrane showed superior resistance to methanol diffusion, as NAFIONTM exhibited a diffusion coefficient about 4-8 times greater than the coefficient of the polyphosphazene membrane.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

L'invention concerne des membranes conductrices de protons présentant une résistance améliorée à la perméation par le méthanol. Cette invention concerne également des procédés de fabrication de ces membranes. Dans un mode de réalisation préféré, les membranes polymères sont formées par a) dissolution d'un polymère, qui est de préférence un polyphosphazène, dans un solvant, de manière à élaborer une solution polymère; b) ajout d'un oxyacide à cette solution polymère; c) ajout éventuel d'eau à cette solution polymère, de préférence selon un rapport molaire équivalent audit oxyacide; d) concentration éventuelle de la solution polymère; e) coulée de cette solution polymère sur une surface de coulée, par exemple une surface fabriquée en ou revêtue de TEFLON TM; et enfin f) élimination de ce solvant organique pour former ladite membrane polymère. Les membranes polymères de cette invention peuvent en particulier être utilisées dans des piles à combustible du type permettant de convertir le méthanol et l'oxygène en énergie électrique.
PCT/US2000/016006 1999-06-11 2000-06-09 Membranes polymeres conductrices de protons WO2000077874A1 (fr)

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AU54803/00A AU5480300A (en) 1999-06-11 2000-06-09 Proton conducting polymer membranes

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US13871099P 1999-06-11 1999-06-11
US60/138,710 1999-06-11

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7074510B2 (en) 2003-12-30 2006-07-11 Hyundai Motor Company Composite ion-exchange membrane, fabrication method of the same, and membrane-electrode assembly, and polymer electrolyte fuel cell having the same
US7297429B2 (en) 2002-07-05 2007-11-20 Gore Enterprise Holdings, Inc. Ionomer for use in fuel cells and method of making same
US7405015B2 (en) 2001-07-05 2008-07-29 Gore Enterprise Holdings, Inc. Ionomer for use in fuel cells and method of making same
CN102324534A (zh) * 2011-08-02 2012-01-18 东华大学 一种具有质子传导性能的聚酰胺膜及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4840856A (en) * 1986-12-26 1989-06-20 Otsuka Kagaku Kabushiki Kaisha Allyl group-containing oligoethyleneoxypolyphosphazenes, process for their preparation, and their use
US5411663A (en) * 1992-03-20 1995-05-02 Micron Separations, Inc. Alcohol-insoluble nylon microporous membranes
US5789106A (en) * 1994-12-01 1998-08-04 Danacell Aps Ion-conductive polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4840856A (en) * 1986-12-26 1989-06-20 Otsuka Kagaku Kabushiki Kaisha Allyl group-containing oligoethyleneoxypolyphosphazenes, process for their preparation, and their use
US5411663A (en) * 1992-03-20 1995-05-02 Micron Separations, Inc. Alcohol-insoluble nylon microporous membranes
US5789106A (en) * 1994-12-01 1998-08-04 Danacell Aps Ion-conductive polymers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7405015B2 (en) 2001-07-05 2008-07-29 Gore Enterprise Holdings, Inc. Ionomer for use in fuel cells and method of making same
US7297429B2 (en) 2002-07-05 2007-11-20 Gore Enterprise Holdings, Inc. Ionomer for use in fuel cells and method of making same
US7074510B2 (en) 2003-12-30 2006-07-11 Hyundai Motor Company Composite ion-exchange membrane, fabrication method of the same, and membrane-electrode assembly, and polymer electrolyte fuel cell having the same
CN102324534A (zh) * 2011-08-02 2012-01-18 东华大学 一种具有质子传导性能的聚酰胺膜及其制备方法

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