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WO2006131758A2 - Membrane electrode assemblies and their production - Google Patents

Membrane electrode assemblies and their production Download PDF

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Publication number
WO2006131758A2
WO2006131758A2 PCT/GB2006/002145 GB2006002145W WO2006131758A2 WO 2006131758 A2 WO2006131758 A2 WO 2006131758A2 GB 2006002145 W GB2006002145 W GB 2006002145W WO 2006131758 A2 WO2006131758 A2 WO 2006131758A2
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Prior art keywords
membrane
assembly according
irradiation
grafting
fuel
Prior art date
Application number
PCT/GB2006/002145
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French (fr)
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WO2006131758A3 (en
Inventor
Donald James Highgate
Keith Victor Lovell
Jacqueline Anne Horsfall
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Itm Power (Research) Ltd.
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Publication of WO2006131758A2 publication Critical patent/WO2006131758A2/en
Publication of WO2006131758A3 publication Critical patent/WO2006131758A3/en

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Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04197—Preventing means for fuel crossover
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • 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

  • Electrochemical cells including solid polymer fuel cells and electrolysers, are typically constructed of a membrane electrode assembly (MEA) which comprises an ionically conducting membrane contained in rigid electrode and manifold structures to deliver the fuel, and rigid metal or graphite bi-polar plates to separate the individual cells in a cell stack.
  • MEA membrane electrode assembly
  • the function of the membrane is to facilitate the transfer of electrically charged ions from one electrode to the other and to maintain separation of the fuel and oxidant streams.
  • the thickness of the operating membrane should be reduced, in order to maximise the efficiency of the resulting cell.
  • This has been the objective of previous membrane technologies irrespective of the fuel to be used, e.g. hydrogen-oxygen, hydrogen-air, alcohol-air alcohol liquid oxidant, or sodium borohydride. For these reasons, the thickness of normal Nafion membranes is in the range 50 to 200 ⁇ m.
  • Fuel and/or oxidant cross-over effectively provides a parasitic loss within the cell, and significantly reduces overall efficiency of operation. While this effect occurs in all types of solid polymer cell operating on any combination of fuels and oxidants, it is of particular importance when using direct alcohol fuel, i.e. a fuel cell system in which alcohol or alcohol water mixture is introduced directly into the anode chamber. In this case, the efficiency of the fuel cell is normally reduced by the cross-over of alcohol through the membrane.
  • a membrane electrode assembly comprises a membrane, a catalyst and an electrode, in which the membrane is obtainable by the steps of
  • an ionically conducting material in the form of a membrane can be achieved in several ways, including mutual grafting or post-irradiation grafting, e.g. using ionising radiation from a gamma source or high energy radiation from an electron beam device.
  • the processes described herein result in the production of a material which is ionically conductive by a two-step procedure, firstly the grafting of an intermediate moiety onto the polymer film, followed by sulphonation of the graft to provide the hydrophilic ion conductive group.
  • the grafted polymer Two techniques have been used to produce the grafted polymer, mutual grafting, whereby the monomer is present during the irradiation and post-irradiation grafting, where the polymer is first irradiated to create radicals which are then subsequently reacted with a monomer.
  • the grafted intermediate moiety is the polymer grafted with styrene, which in itself in hydrophobic. In order for it to become ion- conducting, it has to be further functionalised, e.g. sulphonated.
  • the ionic conductivity of the resulting membrane when made by post-irradiation grafting depends upon a number of factors. These include: (i) the chemical composition of the initial membrane,
  • parameters such as total dose, dose rate, and monomer concentration may be important in determining the properties of the resulting copolymer.
  • typical total doses are 0.5 to 3 Mrad.
  • the dose rate range is 0.0005 to 0.20 Mrad/hr.
  • Monomer concentrations can vary from 10% to 100%.
  • the temperature at which the grafting reaction proceeds may be important, since during this stage a finite number of radicals will be produced in the polymer, determined by the radiation dose and dose rate, the irradiation temperature and atmosphere. Typical temperatures and times used are 40 0 C to 7O 0 C, over 3 to 24 hours.
  • Ethylene- tetrafluoroethylene film was supplied by Nowofol GmbH.
  • Low density polyethylene film LDPE
  • Styrene 99% was supplied by Aldrich® (stabilised with 10-15 ppm 4-tert-butyl catechol).
  • Toluene (SLR grade), methanol (SLR grade) and chlorosulphonic acid were supplied by Fisher Scientific UK. Demineralised water was from a mixed bed Elgastat®, with conductivity ⁇ 50 ⁇ S.
  • Pieces of polymer film (approx. 0.3 m x 0.5 m) were cut, weighed and rolled in a
  • the roll was placed in a glass vessel and the vessel filled with monomer solution. The solution was allowed to soak into the roll for approximately 10 minutes. The oxygen in the vessel was then either removed by purging with nitrogen or by evacuation using a water pump. The whole vessel was then placed in a Cobalt 60 gamma source to be irradiated for a predetermined time, the distance of the tube from the source determining the dose rate. The temperature of the irradiation cell was measured at 23 ⁇ 1 0 C. After irradiation, the vessel was emptied, the roll untied and the grafted films unwrapped from the interlayer.
  • the copolymerised film was washed in toluene for 24 h to remove unreacted or homopolymerised styrene, washed in methanol to remove the toluene, and dried to constant weight in an oven at 7O 0 C.
  • No additional homopolymerisation inhibitor was used in any of the grafting experiments, as the inhibitor present in the styrene (4-tert-butyl catechol) was shown to prevent excessive homopolymerisation.
  • the degree of grafting of the membranes was calculated using the following formula:
  • W 0 weight of polymer film before grafting
  • W 9 weight of grafted copolymer
  • the degree of grafting therefore represents the grafted proportion of the copolymer and has an upper limit of 100%.
  • a copolymer with a graft weight of 50% comprises 50% of the original polymer and 50% graft.
  • the dose rates used were between 500 Gy. h "1 and 50 Gy. h "1 to a total dose of 10 kGy.
  • the total dose range was 10 to 30 kGy.
  • the monomer concentration ranged from 20% to 70% (V/V) in toluene.
  • Sulphonation A Standard sulphonation procedure was carried out on all the polymer films grafted and found to be suitable for all the copolymer types.
  • the grafted polymers were immersed in a solution of chlorosulphonic acid in methylene chloride.
  • the concentration of the chlorosulphonic acid was 2%-5% (V/V) and the sulphonation time ranged from 1-5 h at ambient temperature. After sulphonation, the films were washed to neutrality with demineralised water. Heat-Treatment
  • the membranes were subjected to a thermal annealing process, by being heated at 95 0 C in demineralised water for 1 h and then dried in an oven at 4O 0 C. The process has been found to increase the hydrophilicity and thus ionic conductivity of the grafted membranes.
  • Example 2 Post-irradiation Grafting
  • the polymer films were irradiated in air at 23 ⁇ 1 0 C at a known dose rate and to set total doses. The films were then stored in a freezer at -18 0 C until required.
  • the irradiated films were prepared for grafting by placing pieces of cut and weighed film (approx. 0.3 m x 0.5 m) in a glass vessel and filling with monomer solution. As in Example 1 , no homopolymerisation inhibitor was used. The vessel was purged with nitrogen for 2 h, sealed and placed in a water bath at a set temperature for a known length of time. After grafting, the copolymers were retrieved, washed in toluene, dried to constant weight in the same manner as for the mutual grafts.
  • the polymer films were irradiated to total doses between 15 and 100 kGy.
  • the monomer concentrations ranged from 20% to 80% (V/V).
  • the grafting temperature ranged from 40 to 70 ⁇ 1 0 C.
  • the grafting time ranged from 3 to 24 h. Sulphonation and heat-treatment were then conducted as in Example 1.
  • Results for Example 1 are shown in Table 1. Results for Example 2 are given in Tables 2A and 2B.
  • PSSA refers to the polymer-styrene-sulphonic acid. Table 1

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Graft Or Block Polymers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

A membrane electrode assembly comprises a membrane, a catalyst and an electrode, in which the membrane is obtainable by the steps of (i) forming a polymer film and (ii) reacting the film with a material having strongly ionic groups, to form a polymer film having the ionic groups grafted thereon.

Description

MEMBRANE ELECTRODE ASSEMBLIES AND THEIR PRODUCTION Field of the Invention
This invention relates to membrane electrode assemblies and their production. Background of the Invention Electrochemical cells, including solid polymer fuel cells and electrolysers, are typically constructed of a membrane electrode assembly (MEA) which comprises an ionically conducting membrane contained in rigid electrode and manifold structures to deliver the fuel, and rigid metal or graphite bi-polar plates to separate the individual cells in a cell stack. The function of the membrane is to facilitate the transfer of electrically charged ions from one electrode to the other and to maintain separation of the fuel and oxidant streams. It has been assumed that the thickness of the operating membrane should be reduced, in order to maximise the efficiency of the resulting cell. This has been the objective of previous membrane technologies irrespective of the fuel to be used, e.g. hydrogen-oxygen, hydrogen-air, alcohol-air alcohol liquid oxidant, or sodium borohydride. For these reasons, the thickness of normal Nafion membranes is in the range 50 to 200 μm.
Fuel and/or oxidant cross-over effectively provides a parasitic loss within the cell, and significantly reduces overall efficiency of operation. While this effect occurs in all types of solid polymer cell operating on any combination of fuels and oxidants, it is of particular importance when using direct alcohol fuel, i.e. a fuel cell system in which alcohol or alcohol water mixture is introduced directly into the anode chamber. In this case, the efficiency of the fuel cell is normally reduced by the cross-over of alcohol through the membrane. Summary of the Invention
The present invention is based at least in part on the realisation that, provided that the ionic properties of the membrane can be controlled, a thick membrane may be particularly advantageous in that it reduces the cross-over of fuel and or oxidant from one side of the cell to the other. According to the invention, a membrane electrode assembly comprises a membrane, a catalyst and an electrode, in which the membrane is obtainable by the steps of
(i) forming a polymer film and
(ii) reacting the film with a material having strongly ionic groups, to form a polymer film having the ionic groups grafted thereon. Description of the Invention
In this specification, reference to specific materials will be understood as illustrative only. A variety of polymers can be used, including LDPE and ETFE, and other materials, can be used in the invention, and are known to those of ordinary skill in the art. On irradiation, and grafting with a functional, intermediate molecule such as styrene, functionalisation can be achieved using a material that introduces ionic groups, e.g. by using sulphonic acid groups. They provide the membrane's ionic conductivity.
The production of an ionically conducting material in the form of a membrane can be achieved in several ways, including mutual grafting or post-irradiation grafting, e.g. using ionising radiation from a gamma source or high energy radiation from an electron beam device.
The processes described herein result in the production of a material which is ionically conductive by a two-step procedure, firstly the grafting of an intermediate moiety onto the polymer film, followed by sulphonation of the graft to provide the hydrophilic ion conductive group.
Two techniques have been used to produce the grafted polymer, mutual grafting, whereby the monomer is present during the irradiation and post-irradiation grafting, where the polymer is first irradiated to create radicals which are then subsequently reacted with a monomer. In each case, the grafted intermediate moiety is the polymer grafted with styrene, which in itself in hydrophobic. In order for it to become ion- conducting, it has to be further functionalised, e.g. sulphonated.
The ionic conductivity of the resulting membrane when made by post-irradiation grafting depends upon a number of factors. These include: (i) the chemical composition of the initial membrane,
(ii) the method of irradiation and grafting, (iii) the dose rate and total radiation dose applied, (iv) the treatment of the irradiated polymer membrane prior to exposure to the monomers or polymers that are to be grafted to the membrane, (v) the chemical composition of the graft materials,
(vi) precise details of the subsequent sulphonation process. It is normally found that the degree of grafting, which is related to ionic conductivity of a membrane, varies through the thickness of the membrane, being higher at the surface and decreasing towards the centre. For this reason, thick membranes, e.g. over 75 μm in thickness, are not easily made with high and uniform levels of ionic conductivity as judged by uniformity of graft weight (GW). However, it will now be evident that, based on the knowledge of one of ordinary skill in the art, it is possible by selection of initial membrane material, highly developed post-irradiation graft technology and post-graft sulphonation processes to produce materials which exhibit high conductance as determined by uniformity of graft weight, throughout the thickness of membranes, from 75 μm to 1.0 mm or more in thickness.
For mutual grafting, parameters such as total dose, dose rate, and monomer concentration may be important in determining the properties of the resulting copolymer. For mutual grafting, typical total doses are 0.5 to 3 Mrad. Thus, over periods of typically 20 to 100 hours, then the dose rate range is 0.0005 to 0.20 Mrad/hr. Monomer concentrations can vary from 10% to 100%.
For post-irradiation grafting, the temperature at which the grafting reaction proceeds may be important, since during this stage a finite number of radicals will be produced in the polymer, determined by the radiation dose and dose rate, the irradiation temperature and atmosphere. Typical temperatures and times used are 400C to 7O0C, over 3 to 24 hours.
In the pre-irradiation experiments exemplified, the irradiations were carried out in air at 23+10C in order to produce predominantly peroxy radicals. On heating, these radicals decompose, producing radicals able to react with the monomer. The grafting temperature and time should be chosen accordingly. A high temperature may result in the premature recombination of radicals without grafting, a low temperature will reduce the rate of radical interaction and lower the graft weight. The following Examples illustrate the invention.
All the polymers and reagents were used as received. Ethylene- tetrafluoroethylene film (ETFE) was supplied by Nowofol GmbH. Low density polyethylene film (LDPE) was supplied by Transatlantic Plastics Ltd. Styrene, 99% was supplied by Aldrich® (stabilised with 10-15 ppm 4-tert-butyl catechol). Toluene (SLR grade), methanol (SLR grade) and chlorosulphonic acid were supplied by Fisher Scientific UK. Demineralised water was from a mixed bed Elgastat®, with conductivity <50μS. Example 1
Mutual Grafting
Pieces of polymer film (approx. 0.3 m x 0.5 m) were cut, weighed and rolled in a
'Swiss-Roll' configuration with a non-woven interlayer. The roll was placed in a glass vessel and the vessel filled with monomer solution. The solution was allowed to soak into the roll for approximately 10 minutes. The oxygen in the vessel was then either removed by purging with nitrogen or by evacuation using a water pump. The whole vessel was then placed in a Cobalt 60 gamma source to be irradiated for a predetermined time, the distance of the tube from the source determining the dose rate. The temperature of the irradiation cell was measured at 23 ± 10C. After irradiation, the vessel was emptied, the roll untied and the grafted films unwrapped from the interlayer.
The copolymerised film was washed in toluene for 24 h to remove unreacted or homopolymerised styrene, washed in methanol to remove the toluene, and dried to constant weight in an oven at 7O0C. No additional homopolymerisation inhibitor was used in any of the grafting experiments, as the inhibitor present in the styrene (4-tert-butyl catechol) was shown to prevent excessive homopolymerisation.
The degree of grafting of the membranes was calculated using the following formula:
W - W0
—5 x 100 = Degree of Grafting(%)
wherein W0 = weight of polymer film before grafting, and W9 = weight of grafted copolymer.
The degree of grafting therefore represents the grafted proportion of the copolymer and has an upper limit of 100%. On this basis, a copolymer with a graft weight of 50% comprises 50% of the original polymer and 50% graft.
The dose rates used were between 500 Gy. h"1 and 50 Gy. h"1 to a total dose of 10 kGy. The total dose range was 10 to 30 kGy. The monomer concentration ranged from 20% to 70% (V/V) in toluene. Sulphonation A Standard sulphonation procedure was carried out on all the polymer films grafted and found to be suitable for all the copolymer types. The grafted polymers were immersed in a solution of chlorosulphonic acid in methylene chloride.
The concentration of the chlorosulphonic acid was 2%-5% (V/V) and the sulphonation time ranged from 1-5 h at ambient temperature. After sulphonation, the films were washed to neutrality with demineralised water. Heat-Treatment
Before being used, the membranes were subjected to a thermal annealing process, by being heated at 950C in demineralised water for 1 h and then dried in an oven at 4O0C. The process has been found to increase the hydrophilicity and thus ionic conductivity of the grafted membranes. Example 2 Post-irradiation Grafting
The polymer films were irradiated in air at 23 ± 10C at a known dose rate and to set total doses. The films were then stored in a freezer at -180C until required.
The irradiated films were prepared for grafting by placing pieces of cut and weighed film (approx. 0.3 m x 0.5 m) in a glass vessel and filling with monomer solution. As in Example 1 , no homopolymerisation inhibitor was used. The vessel was purged with nitrogen for 2 h, sealed and placed in a water bath at a set temperature for a known length of time. After grafting, the copolymers were retrieved, washed in toluene, dried to constant weight in the same manner as for the mutual grafts.
The polymer films were irradiated to total doses between 15 and 100 kGy. The monomer concentrations ranged from 20% to 80% (V/V). The grafting temperature ranged from 40 to 70 ± 10C. The grafting time ranged from 3 to 24 h. Sulphonation and heat-treatment were then conducted as in Example 1.
Results for Example 1 are shown in Table 1. Results for Example 2 are given in Tables 2A and 2B. PSSA refers to the polymer-styrene-sulphonic acid. Table 1
Table 2A
Figure imgf000007_0002
Table 2B
Figure imgf000007_0003

Claims

Claims
1. A membrane electrode assembly comprising a membrane, a catalyst and an electrode, in which the membrane is obtainable by the steps of
(i) forming a polymer film and (ii) reacting the film with a material having strongly ionic groups, to form a polymer film having the ionic groups grafted thereon.
2. An assembly according to claim 1 , wherein the graft weight of the membrane is greater than 25%.
3. An assembly according to claim 1 or claim 2, wherein the thickness of the membrane is greater than 100 μm.
4. An assembly according to claim 3, wherein the thickness is 0.25 to 1 mm.
5. An assembly according to any preceding claim, wherein step (ii) comprises irradiation of the film.
6. An assembly according to any preceding claim, wherein the irradiation forms radicals that are reactive with said material.
7. An assembly according to any of claims 1 to 6, wherein said material is present during the irradiation.
8. An assembly according to any of claims 1 to 6, wherein said material is introduced after the irradiation.
9. A method for the production of an assembly according to any of claims 1 to 4, which comprises the said steps.
10. A method according to claim 9, wherein the steps are as defined in any of claims 5 to 8.
11. A fuel cell or electrolyser comprising an assembly according to any of claims 1 to 8.
12. A stack of assemblies according to any of claims 1 to 8.
13. Use of a fuel cell according to claim 11 with a gaseous fuel and/or oxidant.
14. Use of a fuel cell according to claim 11 with a liquid fuel and/or oxidant.
15. Use according to claim 13 or claim 14, wherein the fuel comprises alcohol.
PCT/GB2006/002145 2005-06-10 2006-06-12 Membrane electrode assemblies and their production WO2006131758A2 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008090351A1 (en) * 2007-01-26 2008-07-31 The Secretary Of State For Defence Anion exchange membranes
US9142851B2 (en) 2006-06-13 2015-09-22 Itm Power (Research) Ltd. Composite membranes having a hydrophilic material and a conductive material susceptible to dehydration and their use in electrochemical cells

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5679482A (en) * 1994-05-23 1997-10-21 Dais Corporation Fuel cell incorporating novel ion-conducting membrane
EP1063334A1 (en) * 1999-06-22 2000-12-27 Johnson Matthey Public Limited Company Non-woven fibre webs
US6630518B1 (en) * 1999-02-16 2003-10-07 Mikael Paronen Polymer membrane and a process for the production thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5679482A (en) * 1994-05-23 1997-10-21 Dais Corporation Fuel cell incorporating novel ion-conducting membrane
US6630518B1 (en) * 1999-02-16 2003-10-07 Mikael Paronen Polymer membrane and a process for the production thereof
EP1063334A1 (en) * 1999-06-22 2000-12-27 Johnson Matthey Public Limited Company Non-woven fibre webs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BRACK H P ET AL: "DEVELOPMENT OF RADIATION-GRAFTED MEMBRANES FOR FUEL CELL APPLICATIONS BASED ON POLY(ETHYLENE-ALT-TETRAFLUOROETHYLENE)" STN CAPLUS, 1997, XP002907346 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9142851B2 (en) 2006-06-13 2015-09-22 Itm Power (Research) Ltd. Composite membranes having a hydrophilic material and a conductive material susceptible to dehydration and their use in electrochemical cells
WO2008090351A1 (en) * 2007-01-26 2008-07-31 The Secretary Of State For Defence Anion exchange membranes
GB2458079A (en) * 2007-01-26 2009-09-09 Secr Defence Anion exchange membranes
JP2010516853A (en) * 2007-01-26 2010-05-20 イギリス国 Anion exchange membrane
GB2458079B (en) * 2007-01-26 2012-04-25 Secr Defence Anion exchange membranes

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