WO2010076661A1 - Composite membrane for electrochemical cells - Google Patents

Composite membrane for electrochemical cells Download PDF

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Publication number
WO2010076661A1
WO2010076661A1 PCT/IB2009/008010 IB2009008010W WO2010076661A1 WO 2010076661 A1 WO2010076661 A1 WO 2010076661A1 IB 2009008010 W IB2009008010 W IB 2009008010W WO 2010076661 A1 WO2010076661 A1 WO 2010076661A1
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WO
WIPO (PCT)
Prior art keywords
mat
membrane
fibrils
composite membrane
ionomer
Prior art date
Application number
PCT/IB2009/008010
Other languages
French (fr)
Inventor
Zhijun Gu
Jun Zhai
Original Assignee
Horizon Fuel Cell Technologies Pte. Ltd.
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 Horizon Fuel Cell Technologies Pte. Ltd. filed Critical Horizon Fuel Cell Technologies Pte. Ltd.
Publication of WO2010076661A1 publication Critical patent/WO2010076661A1/en

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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
    • 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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • 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
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/40—Fibre reinforced membranes
    • 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
    • H01M8/1039—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
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of 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 invention relates to a composite membrane for an electrochemical cell, particularly a fuel cell or an electrolyser system, comprising a mat having a microporous structure of fibrils and consisting of expanded polytetrafluoroethylene (ePTFE), and an ionomer filling the pores of the microporous structure of the mat and allowing an ion exchange through the membrane.
  • a composite membrane for an electrochemical cell particularly a fuel cell or an electrolyser system
  • a mat having a microporous structure of fibrils and consisting of expanded polytetrafluoroethylene (ePTFE), and an ionomer filling the pores of the microporous structure of the mat and allowing an ion exchange through the membrane.
  • ePTFE expanded polytetrafluoroethylene
  • a membrane as defined above is known from US 2002/0011684 A1.
  • PTFE polytetrafluoroethylene
  • the resulting product has different tensile strengths in different directions depending on the expansion directions. This results in membranes with non-uniform characteristics.
  • PTFE is extremely hydrophobic and highly mechanically instable. Both make it problematically to add the ionomer to the ePTFE.
  • a surfactant has to be added otherwise the wetting of the microporous structure will be poor and the impregnation will be incomplete.
  • US 4,954,388 describes a multi-layer composite membrane having a film of continuous ionomer and a sheet of ePTFE reinforced by a fabric consisting of fibres of fluoropolymer.
  • the multi-layer structure results in an excessive thickness of the membrane.
  • the composite membrane of the invention is characterized in that the fibrils of the microporous structure of the mat are covered by a film of a polymer, which preferably is a polyimide or a fluoropolymer, the latter being preferable a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV).
  • a polymer which preferably is a polyimide or a fluoropolymer, the latter being preferable a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV).
  • Such membrane has a thickness more or less equal to the thickness of the mat which is a single layer, the cover constitutes a reinforcement which provides for a high tensile strength in all directions and, if a polymer with good wetting properties is chosen, the surfactant in the process of applying the ionomer to the mat can be reduced or dispensed with, allowing a higher process speed and, if desired, a higher water content in the solution of the ionomer before applying it. Further if such membrane is used into an electrolyser cell it allows to apply a pressure difference directly in the cell.
  • Fig. 1 is a magnified cross section through a membrane of the invention, with an even more magnified extract.
  • Fig. 2 is a perspective view of three fibrils of a mat contained in the membrane connected by a node.
  • a composite membrane 1 consists of a mat 2 of fibrils 3 connected by nodes 4 or connected otherwise as known from US RE 37,701 E, so as to constitute some sort of a scaffold or skeleton of the membrane 1 , serving as a support structure, and of an ionomer 5.
  • the mat 2 has a structure of a non- woven tangle of fibrils 3 having irregular cavities in-between which constitute micro-pores of an average pore size e.g. 0,2 ⁇ m leading to a porosity of the mat of 85 to 90% and a thickness of 3 ⁇ m.
  • the fibrils 3 consists of expanded polytetrafluoroethylene (ePTFE).
  • the ionomer 5 is introduced into the micro-pores and also applied to both surfaces of the mat 2 so as to result in an air-tight membrane. In a manner known per se.
  • the ionomer dissolved in a solvent is uniformly applied so as to impregnate and occlude the micro-pores of the mat 2.
  • a reinforcing and easily wettable material 10 is applied to the fibrils 3 and nodes 4 of the mat 2 thereby forming a cover, such material 10 fulfilling the tasks of being non-pollutant to the electrochemical cells, increasing the tensile strength of the ePTFE and changing the surface properties of the fibrils 3 making them easier wettable.
  • Such material 10 according to the described example is THV, which is a terpolymer of the three components tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, or a polyimide. It is applied in a solution or dispersion with reference to the task to fill the micro-pores of the mat 2 without breaking them .
  • acetone is chosen for THV or N- Methylpyrrolidon (NMP) for polyimide.
  • NMP N- Methylpyrrolidon
  • the solution is applied to the fibrils 3 using standard processes like sputtering with or without air, immerse or screen printing, preferable sputtering with an ultrasonic nebulizer.
  • the solvent will then be evaporated without destroying the structure of the mat 2 using a temperature depending on the chosen material 10.
  • a temperature slightly above of its melting temperature, preferably melting temperature + 15°C can be used, thus sintering the fibrils 3 and solidifying the resulting cover of the fibrils 3 especially if the mat 2 comprises nodes 4. This enlarges the mechanical stability because the fibrils 3 will be tougher enclosed by the material 10 and stick even closer together.
  • the mass ratio between the fibrils 3 and the material 10 of the cover can be 500:5 and preferably is 10:3.
  • the composite membrane 1 resulting from the above method has high mechanical stability with uniform tensile strength, especially the shrinking and swelling properties are less intensive compared with conventional membranes thus allowing an easier handling e.g. of sealing techniques if assembled in electrochemical cells. Further it can be manufactured at higher speed due to no need of a surfactant and due to the possible higher rate of water in the ionomer solution because of the different hydrophobic character of the material 10 that covers the fibrils 3.
  • the composite membrane 1 further is free of cavities, also due to the less hydrophobic character of material 10 and a lower grade ePTFE, i.e. with less mechanical strength, as material for the mat 2 can be used, thus saving costs.
  • the composite membrane 1 is used in an electrolyser cell, a pressure difference can be applied on both sides of the membrane 1 thus resulting in an easier, less complicated system arrangement.
  • the mat 2 UD160F from the company Uno-Tech Ltd., Shanghai with a thickness of 3 ⁇ m, a porosity of > 85 % and a pore diameter of 0,1 to 1 ⁇ m is supplied.
  • the mat 2 is mounted onto a frame so that both major surfaces are not in contact with other bodies.
  • the frame is then positioned about 3 cm above a heating plate which is heated to 100°C and under a ultrasonic nebulizer.
  • a suspension will be supplied to the ultrasonic nebulizer for sputtering onto the upper surface of the mat 2.
  • the suspension consists of 3 wt% of THV220G, a fluoroelastomer from Dyneon, Inc. of Oakdale, Minn., USA with a specific gravity of 1.95 and a melting temperature of 124°C, mixed in acetone.
  • THV400G or THV500G from Dyneon can be supplied wherein the different melting temperatures of 150 to 160°C respectively 162 to174°C is to be considered.
  • the sputtering itself will be supplied in one cross-way by meaning of sputtering the suspension from left to right in lines and then from up to down in columns, so the suspension is applied into the micro-pores of the mat 2 and is not maintained on the surface of the mat 2 neither trickles through the mat 2 onto the heating plate.
  • the heating plate has the task to dry off the acetone in one process step almost at the same time with the sputtering step.
  • the next step is a sintering process at 150 °C for 15 min.
  • the mat 2 including the now reinforced fibrils 3 with the reinforcement material 10 consists of 10wt% ePTFE reinforced with a total of 2,7wt% THV, comprising a total porosity of about 87,3 % (the different specific gravities of THV and ePTFE being neglected for an easier calculation).
  • the ionomer ⁇ will be sputtered onto the cover of the reinforced mat 2 which is still placed in the frame, again using an ultrasonic nebulizer.
  • the ionomer comprises 10 wt% of Nafion® in water commercially available by DuPont Co and an alcohol, preferred ethanol; the both components are mixed so that the resulting solution or dispersion comprises a total of 5 wt% of Nafion®.
  • the ionomer solution is now sputtered onto the mat 2 in one cross- way.
  • the last production step now comprises a drying process for 120 min at 100°C and a sintering process for 60 min at 150°C.
  • this cheap membrane can e.g. achieve 650 mA/cm 2 at 0.6V and 58 °C.

Abstract

A composite membrane (1) for an electrochemical cell, i.e. a fuel cell or electrolyser system, is described which comprises a mat (2) having a microporous structure of fibrils (3) which consist of expanded polytetrafluoroethylene (ePTFE) and are covered by a film of a polymer (10), especially polyimide or THV, and further comprises an ionomer (5) filling the pores of the microporous structure of the mat and allowing an ion exchange through the membrane.

Description

COMPOSITE MEMBRANE FOR ELECTROCHEMICAL CELLS
FIELD OF THE INVENTION
The invention relates to a composite membrane for an electrochemical cell, particularly a fuel cell or an electrolyser system, comprising a mat having a microporous structure of fibrils and consisting of expanded polytetrafluoroethylene (ePTFE), and an ionomer filling the pores of the microporous structure of the mat and allowing an ion exchange through the membrane.
BACKGROUND OF THE INVENTION
A membrane as defined above is known from US 2002/0011684 A1. When expanding polytetrafluoroethylene (PTFE), the resulting product has different tensile strengths in different directions depending on the expansion directions. This results in membranes with non-uniform characteristics. PTFE is extremely hydrophobic and highly mechanically instable. Both make it problematically to add the ionomer to the ePTFE. Thus, for impregnating the microporous structure with the ionomer material, a surfactant has to be added otherwise the wetting of the microporous structure will be poor and the impregnation will be incomplete.
US 4,954,388 describes a multi-layer composite membrane having a film of continuous ionomer and a sheet of ePTFE reinforced by a fabric consisting of fibres of fluoropolymer. The multi-layer structure results in an excessive thickness of the membrane.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a thin composite membrane having a uniform, high tensile strength in all directions which membrane can be prepared without or with reduced use of a surfactant. To attain this object, the composite membrane of the invention is characterized in that the fibrils of the microporous structure of the mat are covered by a film of a polymer, which preferably is a polyimide or a fluoropolymer, the latter being preferable a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV). Such membrane has a thickness more or less equal to the thickness of the mat which is a single layer, the cover constitutes a reinforcement which provides for a high tensile strength in all directions and, if a polymer with good wetting properties is chosen, the surfactant in the process of applying the ionomer to the mat can be reduced or dispensed with, allowing a higher process speed and, if desired, a higher water content in the solution of the ionomer before applying it. Further if such membrane is used into an electrolyser cell it allows to apply a pressure difference directly in the cell.
BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and further objects, features and advantages of the present invention will become apparent from the following description of a preferred embodiment with reference to the accompanying drawings. Fig. 1 is a magnified cross section through a membrane of the invention, with an even more magnified extract.
Fig. 2 is a perspective view of three fibrils of a mat contained in the membrane connected by a node.
DETAILED DESCRIPTION OF A PREFERRED EMBOMENT A composite membrane 1 consists of a mat 2 of fibrils 3 connected by nodes 4 or connected otherwise as known from US RE 37,701 E, so as to constitute some sort of a scaffold or skeleton of the membrane 1 , serving as a support structure, and of an ionomer 5. The mat 2 has a structure of a non- woven tangle of fibrils 3 having irregular cavities in-between which constitute micro-pores of an average pore size e.g. 0,2 μm leading to a porosity of the mat of 85 to 90% and a thickness of 3μm. The fibrils 3 consists of expanded polytetrafluoroethylene (ePTFE). For completing the mat 2 to a composite membrane 1 , the ionomer 5 is introduced into the micro-pores and also applied to both surfaces of the mat 2 so as to result in an air-tight membrane. In a manner known per se. The ionomer dissolved in a solvent is uniformly applied so as to impregnate and occlude the micro-pores of the mat 2.
Before applying the ionomer 5, a reinforcing and easily wettable material 10 is applied to the fibrils 3 and nodes 4 of the mat 2 thereby forming a cover, such material 10 fulfilling the tasks of being non-pollutant to the electrochemical cells, increasing the tensile strength of the ePTFE and changing the surface properties of the fibrils 3 making them easier wettable. Such material 10 according to the described example is THV, which is a terpolymer of the three components tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, or a polyimide. It is applied in a solution or dispersion with reference to the task to fill the micro-pores of the mat 2 without breaking them . As solvent ketones, preferably acetone is chosen for THV or N- Methylpyrrolidon (NMP) for polyimide. The solution is applied to the fibrils 3 using standard processes like sputtering with or without air, immerse or screen printing, preferable sputtering with an ultrasonic nebulizer. The solvent will then be evaporated without destroying the structure of the mat 2 using a temperature depending on the chosen material 10. In a next non-mandatory step especially if THV serves as material 10 a temperature slightly above of its melting temperature, preferably melting temperature + 15°C, can be used, thus sintering the fibrils 3 and solidifying the resulting cover of the fibrils 3 especially if the mat 2 comprises nodes 4. This enlarges the mechanical stability because the fibrils 3 will be tougher enclosed by the material 10 and stick even closer together. The mass ratio between the fibrils 3 and the material 10 of the cover can be 500:5 and preferably is 10:3.
The composite membrane 1 resulting from the above method has high mechanical stability with uniform tensile strength, especially the shrinking and swelling properties are less intensive compared with conventional membranes thus allowing an easier handling e.g. of sealing techniques if assembled in electrochemical cells. Further it can be manufactured at higher speed due to no need of a surfactant and due to the possible higher rate of water in the ionomer solution because of the different hydrophobic character of the material 10 that covers the fibrils 3. The composite membrane 1 further is free of cavities, also due to the less hydrophobic character of material 10 and a lower grade ePTFE, i.e. with less mechanical strength, as material for the mat 2 can be used, thus saving costs.
If the composite membrane 1 is used in an electrolyser cell, a pressure difference can be applied on both sides of the membrane 1 thus resulting in an easier, less complicated system arrangement.
EXAMPLE:
As the mat 2 UD160F from the company Uno-Tech Ltd., Shanghai, with a thickness of 3μm, a porosity of > 85 % and a pore diameter of 0,1 to 1 μm is supplied. The mat 2 is mounted onto a frame so that both major surfaces are not in contact with other bodies. The frame is then positioned about 3 cm above a heating plate which is heated to 100°C and under a ultrasonic nebulizer.
A suspension will be supplied to the ultrasonic nebulizer for sputtering onto the upper surface of the mat 2. The suspension consists of 3 wt% of THV220G, a fluoroelastomer from Dyneon, Inc. of Oakdale, Minn., USA with a specific gravity of 1.95 and a melting temperature of 124°C, mixed in acetone. Alternatively THV400G or THV500G from Dyneon can be supplied wherein the different melting temperatures of 150 to 160°C respectively 162 to174°C is to be considered. The sputtering itself will be supplied in one cross-way by meaning of sputtering the suspension from left to right in lines and then from up to down in columns, so the suspension is applied into the micro-pores of the mat 2 and is not maintained on the surface of the mat 2 neither trickles through the mat 2 onto the heating plate. The heating plate has the task to dry off the acetone in one process step almost at the same time with the sputtering step.
The next step is a sintering process at 150 °C for 15 min. The mat 2 including the now reinforced fibrils 3 with the reinforcement material 10 consists of 10wt% ePTFE reinforced with a total of 2,7wt% THV, comprising a total porosity of about 87,3 % (the different specific gravities of THV and ePTFE being neglected for an easier calculation).
In a last step the ionomerδ will be sputtered onto the cover of the reinforced mat 2 which is still placed in the frame, again using an ultrasonic nebulizer. The ionomer comprises 10 wt% of Nafion® in water commercially available by DuPont Co and an alcohol, preferred ethanol; the both components are mixed so that the resulting solution or dispersion comprises a total of 5 wt% of Nafion®. The ionomer solution is now sputtered onto the mat 2 in one cross- way. The last production step now comprises a drying process for 120 min at 100°C and a sintering process for 60 min at 150°C.
In a single hydrogen-air fuel cell with dry gases and nearby ambient pressure for air wherein hydrogen is applied at 0.4 bars, this cheap membrane can e.g. achieve 650 mA/cm2 at 0.6V and 58 °C.

Claims

1. A composite membrane (1) for an electrochemical cell, comprising a mat (2) having a microporous structure of fibrils (3) and consisting of expanded polytetrafluoroethylene (ePTFE), and an ionomer filling the pores of the microporous structure of the mat and allowing an ion exchange through the membrane, characterized in that the fibrils (3) of the microporous structure of the mat (2) are covered by a film of a polymer (10).
2. The membrane according to claim 1 , characterized in that the polymer (10) is a polyimide.
3. The membrane according to claim 1 , characterized in that the polymer (10) is a fluoropolymer.
4. The membrane according to claim 3, characterized in that the fluoropolymer is a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV).
PCT/IB2009/008010 2008-12-30 2009-12-21 Composite membrane for electrochemical cells WO2010076661A1 (en)

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Application Number Priority Date Filing Date Title
CNCN200810205082.8 2008-12-30
CN200810205082A CN101771153A (en) 2008-12-30 2008-12-30 Compound film of electrochemical cell

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Cited By (5)

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EP3076465A1 (en) * 2013-11-29 2016-10-05 Asahi Kasei Kabushiki Kaisha Polymer electrolyte membrane
US10688448B2 (en) 2013-11-29 2020-06-23 Daikin Industries, Ltd. Porous body, polymer electrolyte membrane, filter material for filter, and filter unit
US10930913B2 (en) * 2018-01-09 2021-02-23 Samsung Electronics Co., Ltd. Composite membrane, anode structure including the composite membrane, lithium battery including the anode structure, and method of preparing the composite membrane
US10944121B2 (en) 2013-11-29 2021-03-09 Asahi Kasei Kabushiki Kaisha Polymer electrolyte film
US11084895B2 (en) 2013-11-29 2021-08-10 Daikin Industries, Ltd. Modified polytetrafluoroethylene fine powder and uniaxially stretched porous body

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JP6638675B2 (en) * 2017-03-03 2020-01-29 トヨタ自動車株式会社 Fuel cell catalyst ink, fuel cell catalyst layer, and membrane electrode assembly

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US6277512B1 (en) * 1999-06-18 2001-08-21 3M Innovative Properties Company Polymer electrolyte membranes from mixed dispersions
US20020011684A1 (en) 1994-11-14 2002-01-31 Bamdad Bahar Ultra-thin integral composite membrane
USRE37701E1 (en) 1994-11-14 2002-05-14 W. L. Gore & Associates, Inc. Integral composite membrane
US20060201874A1 (en) * 2005-03-11 2006-09-14 Bha Technologies, Inc. Composite membrane
US20070243446A1 (en) * 2005-09-19 2007-10-18 3M Innovative Properties Company Fuel cell electrolyte membrane with acidic polymer
WO2007128247A1 (en) * 2006-05-10 2007-11-15 Horizon Fuel Cells Technologies (Shanghai) Co., Ltd. A novel membrane electrode assembly and its manufacturing process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4954388A (en) 1988-11-30 1990-09-04 Mallouk Robert S Fabric reinforced composite membrane
US20020011684A1 (en) 1994-11-14 2002-01-31 Bamdad Bahar Ultra-thin integral composite membrane
USRE37701E1 (en) 1994-11-14 2002-05-14 W. L. Gore & Associates, Inc. Integral composite membrane
US6277512B1 (en) * 1999-06-18 2001-08-21 3M Innovative Properties Company Polymer electrolyte membranes from mixed dispersions
US20060201874A1 (en) * 2005-03-11 2006-09-14 Bha Technologies, Inc. Composite membrane
US20070243446A1 (en) * 2005-09-19 2007-10-18 3M Innovative Properties Company Fuel cell electrolyte membrane with acidic polymer
WO2007128247A1 (en) * 2006-05-10 2007-11-15 Horizon Fuel Cells Technologies (Shanghai) Co., Ltd. A novel membrane electrode assembly and its manufacturing process

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3076465A1 (en) * 2013-11-29 2016-10-05 Asahi Kasei Kabushiki Kaisha Polymer electrolyte membrane
EP3076465A4 (en) * 2013-11-29 2017-05-10 Asahi Kasei Kabushiki Kaisha Polymer electrolyte membrane
US10644339B2 (en) 2013-11-29 2020-05-05 Asahi Kasei Kabushiki Kaisha Polymer electrolyte membrane
US10688448B2 (en) 2013-11-29 2020-06-23 Daikin Industries, Ltd. Porous body, polymer electrolyte membrane, filter material for filter, and filter unit
US10944121B2 (en) 2013-11-29 2021-03-09 Asahi Kasei Kabushiki Kaisha Polymer electrolyte film
US11084895B2 (en) 2013-11-29 2021-08-10 Daikin Industries, Ltd. Modified polytetrafluoroethylene fine powder and uniaxially stretched porous body
US10930913B2 (en) * 2018-01-09 2021-02-23 Samsung Electronics Co., Ltd. Composite membrane, anode structure including the composite membrane, lithium battery including the anode structure, and method of preparing the composite membrane

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