WO2000024796A1 - Materiaux conducteurs d'ions pour l'electrochimie et procedes correspondants - Google Patents

Materiaux conducteurs d'ions pour l'electrochimie et procedes correspondants

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Publication number
WO2000024796A1
WO2000024796A1 PCT/US1999/019470 US9919470W WO0024796A1 WO 2000024796 A1 WO2000024796 A1 WO 2000024796A1 US 9919470 W US9919470 W US 9919470W WO 0024796 A1 WO0024796 A1 WO 0024796A1
Authority
WO
WIPO (PCT)
Prior art keywords
ion
conducting material
pek
sulfonated
ppsu
Prior art date
Application number
PCT/US1999/019470
Other languages
English (en)
Other versions
WO2000024796A8 (fr
Inventor
Richard M. Formato
Paul Osenar
Robert F. Kovar
Nelson Landrau
Original Assignee
Foster-Miller, Inc.
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
Priority claimed from PCT/US1998/017898 external-priority patent/WO1999010165A1/fr
Application filed by Foster-Miller, Inc. filed Critical Foster-Miller, Inc.
Priority to EP99965719A priority Critical patent/EP1115769A1/fr
Priority to CA002342221A priority patent/CA2342221A1/fr
Priority to JP2000578363A priority patent/JP2003503510A/ja
Priority to AU21424/00A priority patent/AU2142400A/en
Publication of WO2000024796A1 publication Critical patent/WO2000024796A1/fr
Publication of WO2000024796A8 publication Critical patent/WO2000024796A8/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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • 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
    • B01D67/0093—Chemical modification
    • B01D67/00933—Chemical modification by addition of a layer chemically bonded to the membrane
    • 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
    • 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
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • 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
    • B01D71/52—Polyethers
    • 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
    • B01D71/52—Polyethers
    • B01D71/522—Aromatic polyethers
    • B01D71/5221—Polyaryletherketone
    • 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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • 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
    • C08J5/2275—Heterogeneous membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M8/10—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
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, 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
    • H01M8/1039—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
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    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/10—Fuel cells with solid electrolytes
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    • 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
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    • 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
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such 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
    • Y02E60/10—Energy storage using batteries
    • 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
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    • 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
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    • 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

  • This invention relates to novel ion-conducting materials suitable for use as solid polymer electrolyte membranes in electrochemical applications including fuel cell systems. More specifically, these novel ion-conducting polymers are based on sulfonated polyaryletherketone polymers or sulfonated polyphenylsulfone polymers, including copolymers, or blends thereof. The present invention also describes novel processes for producing these ion- conducting materials.
  • Fuel cells are highly efficient electrochemical energy conversion devices that directly convert the chemical energy derived from renewable fuel into electrical energy.
  • Proton-exchange membrane fuel cells have a polymer electrolyte membrane disposed between a positive electrode (cathode) and a negative electrode (anode).
  • the polymer electrolyte membrane is composed of an ion-exchange polymer (i.e., ionomer). Its role is to provide a means for ionic transport and prevent mixing of the molecular forms of the fuel and the oxidant.
  • Solid polymer electrolyte fuel cells are an ideal source of quiet, efficient, and lightweight power. While batteries have reactants contained within their structure which eventually are used up, fuel cells use air and hydrogen to operate continuously. Their fuel efficiency is high (45 to 50 percent), they do not produce noise, operate over a wide power range (10 watts to several hundred kilowatts), and are relatively simple to design, manufacture and operate. Further, SPEFCs currently have the highest power density of all fuel cell types. In addition, SPEFCs do not produce any environmentally hazardous emissions such as NO x and SO x (typical combustion by-products).
  • the traditional SPEFC contains a solid polymer ion-exchange membrane that lies between two gas diffusion electrodes, an anode and a cathode, each commonly containing a metal catalyst supported by an electrically conductive material.
  • the gas diffusion electrodes are exposed to the respective reactant gases, the reductant gas and the oxidant gas.
  • An electrochemical reaction occurs at each of the two junctions (three phase boundaries) where one of the electrodes, electrolyte polymer membrane and reactant gas interface.
  • Ion exchange membranes play a vital role in various electrochemical applications, including that of SPEFCs.
  • the ion- exchange membrane has two functions: (1) it acts as the electrolyte that provides ionic communication between the anode and cathode; and (2) it serves as a separator for the two reactant gases (e.g., O 2 and H 2 ).
  • the ion- exchange membrane while serving as a good proton transfer membrane, must also have low permeability for the reactant gases to avoid cross-over phenomena that reduce performance of the fuel cell. This is especially important in fuel cell applications in which the reactant gases are under pressure and the fuel cell is operated at elevated temperatures.
  • Fuel cell reactants are classified as oxidants and reductants on the basis of their electron acceptor or electron donor characteristics.
  • Oxidants include pure oxygen, oxygen-containing gases (e.g., air) and halogens (e.g., chlorine).
  • Reductants include hydrogen, carbon monoxide, natural gas, methane, ethane, formaldehyde and methanol.
  • Optimized proton and water transports of the membrane and proper water management are also crucial for efficient fuel cell application. Dehydration of the membrane reduces proton conductivity, and excess water can lead to swelling of the membranes. Inefficient removal of by-product water can cause flooding of the electrodes hindering gas access. Both of these conditions lead to poor cell performance.
  • SPEFCs have not yet been commercialized due to unresolved technical problems and high overall cost.
  • One major deficiency impacting the commercialization of the SPEFC is the inherent limitations of today's leading membrane and electrode assemblies.
  • the membranes employed must operate at elevated/high temperatures (>120°C) so as to provide increased power density, and limit catalyst sensitivity to fuel impurities. This would also allow for applications such as on-site cogeneration (high quality waste heat in addition to electrical power).
  • Current membranes also allow excessive methanol crossover in liquid feed direct methanol fuel cells (dependent on actual operating conditions, but is typically equivalent to a current density loss of about 50 to 200 mA/cm 2 @ 0.5 V).
  • fuel crossover is a parasitic reaction that lowers efficiency, reduces performance and generates heat in the fuel cell. It is highly desirable to minimize the rate of fuel crossover.
  • the Nafion® membrane technology is well known in the art and is described in U.S. Patent Nos. 3,282,875 and 4,330,654.
  • Unreinforced Nafion® membranes are used almost exclusively as the ion exchange membrane in present SPEFC applications.
  • This membrane is fabricated from a copolymer of tetrafluoroethylene (TFE) and a perfluorovinyl ethersulfonyl fluoride.
  • the vinyl ether comonomer is copolymerized with TFE to form a melt- processable polymer. Once in the desired shape, the sulfonyl fluoride group is hydrolyzed into the ionic sulfonate form.
  • the fluorocarbon component and the ionic groups are incompatible or immiscible (the former is hydrophobic, the latter is hydrophilic). This causes a phase separation, which leads to the formation of interconnected hydrated ionic "clusters".
  • the properties of these clusters determine the electrochemical characteristics of the polymer, since protons are conducted through the membrane as they "hop" from one ionic cluster to another. To ensure proton flow, each ionic group needs a minimum amount of water to surround it and form a cluster. If the ionic group concentration is too low (or hydration is insufficient) proton transfer will not occur. At higher ionic group concentrations (or increased hydration levels) proton conductivity is improved, but membrane mechanical characteristics are sacrificed.
  • Nafion® membranes There are several mechanisms that limit the performance of Nafion® membranes in fuel cell environments and other electrochemical applications.
  • Nafion® is sensitive to heat and can only be used effectively to temperatures of about 100°C. In fact, performance-limiting phenomenon may begin even at temperatures of about 80°C.
  • Mechanisms which limit the performance of Nafion® include membrane dehydration, reduction of ionic conductivity, radical formation in the membrane (which can destroy the solid polymer electrolyte membrane chemically), loss of mechanical strength via softening, and increased parasitic losses through high fuel permeation.
  • Methanol- crossover not only lowers fuel utilization efficiency but also adversely affects the oxygen cathode performance, significantly lowering cell performance. More specifically, this crossover causes a mixed reaction (oxidation and reduction) to develop on the cathode side, reducing the reaction efficiency.
  • the Nafion® membrane/electrode is also very expensive to produce, and as a result it is not (yet) commercially viable. Reducing membrane cost is crucial to the commercialization of SPEFCs. It is estimated that membrane cost must be reduced by at least an order of magnitude from the Nafion® model for SPEFCs to become commercially attractive.
  • Gore-Select® Another type of ion-conducting membrane, Gore-Select® (commercially available from W.L. Gore), is currently being developed for fuel cell applications. Gore-Select® membranes are further detailed in a series of U.S. Patents (U.S. 5,635,041, 5,547,551 and 5,599,614).
  • Gore discloses a composite membrane consisting of a porous Teflon® film filled with a Nafion® or Nafion®-like ion-conducting solution. Although it has been reported to show high ionic conductance and greater dimensional stability than Nafion® membranes, the Teflon® and Nafion® materials selected and employed by Gore as the film substrate and the ion-exchange material, respectively, may not be appropriate for operation in high-temperature SPEFCs. Teflon® undergoes extensive creep at temperatures above 80°C, and Nafion® and similar ionomers swell and soften above the same temperature. This can result in the widening of interconnected channels in the membrane and allow performance degradation, especially at elevated temperatures and pressures.
  • Gore-Select® as well as many other types of perfluorinated ion- conducting membranes (e.g., Aciplex from Asahi Chemical, Flemion® from Asahi Glass, Japan), are just as costly as Nafion®, since these membranes employ a high percentage of perfluorinated ionomers.
  • ion-exchange membranes that are less expensive to produce also have been investigated for use in polymer electrolyte membrane fuel cells.
  • Poly(trifluorostyrene) copolymers have been studied as membranes for use in polymer electrolyte membrane fuel cells. See e.g., U.S. Patent No. 5,422,411. However, these membranes are suspected to have poor mechanical and film forming properties. In addition, these membranes may be expensive due to the inherent difficulties in processing fluorinated polymers.
  • Sulfonated polyaromatic based systems such as those described in U.S. Patent Nos. 3,528,858 and 3,226,361, also have been investigated as membrane materials for SPEFCs. However, these materials suffer from poor chemical resistance and mechanical properties that limit their use in SPEFC applications.
  • Solid polymer membranes comprising a sulfonated poly(2,6 dimethyl 1 ,4 phenylene oxide) alone or blended with poly(vinylidene fluoride) also have been investigated. These membranes are disclosed in WO 97/24777. However, these membranes are known to be especially vulnerable to degradation from peroxide radicals.
  • PES Sulfonated ⁇ oly(aryl ether ketone)
  • U.S. Patent No. 4,268,650 also describes sulfonated PEK polymers.
  • the process disclosed in this patent relies on the copolymerization of PEK and polyether ether ketone (PEEK) to control the level of sulfonation in concentrated sulfuric acid. Sulfonation under these conditions is thought to occur exclusively at the ether-phenyl-ether linkages.
  • PEEK polyether ether ketone
  • U.S. Patent No. 4,273,903 involves a similar process using polyarylethersulphone copolymers. Specifically, this patent discloses the controllable sulfonation of polyarylethersulphone polymers in concentrated sulfuric acid using copolymers of polyetherether sulfone (sulfonatable) and polyethersulfone (less susceptible to sulfonation). This patent also reports that the use of sulfuric acid/oleum, oleum or chlorosulfonic acid will completely sulfonate and/or degrade the polyethersulfone polymer. The sulfonation procedure described in this reference is carried out homogeneously (i.e., putting the polymer into solution before addition of the sulfonating agent.)
  • U.S. Patent No. 5,795,496 discloses methods for producing sulfonated polyether ether ketone (PEEK) and sulfonated poly (p-phenylene ether sulfone) (PES) polymer materials for use in fuel cells.
  • Target properties of the asymmetric membranes formed using the materials and methods of this patent include a target membrane thickness of 0.05-0.5 mm (equivalent to about 2-20 mils).
  • This patent also reports that thinner membranes, e.g., less than 0.05 mm, have poor mechanical strength and dimensional stability.
  • This reference also describes cross-linking of these sulfonated polymer materials at temperatures of about 120°C for an unspecified time in order to minimize fuel crossover.
  • 4,413,106 provides methods for the heterogeneous sulfonation (i.e., sulfonation of the precipitated polymer/solvent co-crystals) for polyarylethersulfone (PES) polymers in chlorinated hydrocarbon solvents with a sulfonating agent.
  • PES polyarylethersulfone
  • PES polymers of formula (PH-SO 2 -Ph-O) are known to crystallize from a variety of solvents, such as CH 2 C1 2 , DMF, DMAc. The crystallization is promoted by agitation or addition of non-solvents, and is highly dependent upon reaction conditions. Polymer/solvent intercrystallites ( ⁇ 1 micron diameter) form as a suspension in a surplus amount of the solvent. The amount of sulfonating agent added controls the degree of sulfonation. Temperatures are indicated as being preferable from -10 to 25°C.
  • U.S. Patent No. 5,013,765 reports the controllable sulfonation of aromatic PES polymers using sulfur trioxide (sulfonating agent) and sulfuric acid (solvent).
  • sulfuric acid content must be less than 6% wt (based upon the solvent) and that the temperature must be ⁇ 30°C in order to control side reactions and degradation.
  • Chlorosulfonic acid and oleum as sulfonating agents are discouraged since they can lead to an excessive degree of sulfonation and/or polymer degradation.
  • this patent indicates that controllable sulfonation using these agents is not possible.
  • This patent also reports that use of sulfur trioxide in concentrated sulfuric acid can produce sulfonated polymers without by-products or degradation products, especially in the case of O-Ph-SO 2 - Ph based polymers.
  • a central object of the present invention is to provide novel ion- conducting materials suitable for use in a broad range of electrochemical applications, including fuel cell systems.
  • these novel ion-conducting materials are based on sulfonated polyaryletherketone (PEK) homopolymers or PEK copolymers, or blends thereof.
  • these novel ion- conducting materials are based on sulfonated polyphenylsulfone (PPSU) homopolymers or PPSU copolymers, or blends thereof.
  • the class of PEK and PPSU homopolymers, copolymers, and blends thereof disclosed herein may include any desired substituents, provided that such substituents do not substantially impair properties desired for the intended use of the polymer, as may readily be determined by one of ordinary skill in the art. Such properties may include ionic conductivity, chemical and structural stability, swelling properties and so forth. Accordingly, as used herein, PEK and PPSU homopolymers, copolymers and blends thereof, include both substituted and unsubstituted PEK and PPSU polymers.
  • Another object of this invention is to provide novel processes for producing such ion-conducting materials.
  • One preferred ion-conducting material in accordance with the present invention comprises at least one polyaryletherketone (PEK) homopolymer or at least one PEK copolymer, or blends thereof (sometimes referred to hereinafter as "PEK based ion-conducting materials"), wherein the PEK homopolymer is sulfonated and the ion-conducting material is devoid of ether-phenyl-ether linkages.
  • PEK polyaryletherketone
  • the PEK homopolymer comprises repeating units of the formula
  • phenyl rings may be substituted or unsubstituted.
  • the PEK based ion-conducting materials have an IEC from at least about 0.5 meq. ⁇ g to at least about 4 meq./g.
  • the PEK based ion-conducting materials may further comprise sulfone crosslinkages and/or antioxidants.
  • the PEK based ion-conducting materials of the present invention may be halogenated, e.g., brominated or chlorinated, in order to further enhance stability.
  • the PEK based ion-conducting materials of the present invention are useful in the preparation of solid polymer electrolyte membranes.
  • One preferred method of producing ion-conducting materials devoid of ether-phenyl-ether linkages suitable for use in electrochemical applications in accordance with the present invention comprises: providing a solution of at least one PEK homopolymer; adding a sulfonating agent to the PEK homopolymer solution to form a sulfonated PEK homopolymer; and isolating the sulfonated PEK homopolymer from the solution.
  • Preferred sulfonating agents for use in this method comprise at least one of sulfur trioxide, concentrated sulfuric acid and fuming sulfuric acid. In some methods, it is preferred that the sulfonating agent has a free sulfur trioxide content of about 0 (about 100% sulfuric acid) to about 30 wt.% (about 70% sulfuric acid).
  • the PEK homopolymer solution is maintained at a reaction temperature from about 10°C to about 60°C.
  • One preferred method of isolating the sulfonated PEK based ion- conducting material comprises re-precipitating the sulfonated PEK homopolymer into water, water saturated with sodium chloride, methanol or other non-solvent.
  • antioxidants are added to the sulfonated PEK homopolymer, either prior to or following isolation of the sulfonated PEK homopolymer.
  • the PEK based ion-conducting materials are crosslinked, particularly when the ion-conducting material is in the H+ (acid) form.
  • the PEK based ion-conducting material undergoes a halogenation step.
  • Another ion-conducting material in accordance with the present invention comprises at least one sulfonated polyphenylsulfone (PPSU) homopolymer or PPSU copolymer or blends thereof (sometimes referred to hereinafter as "PPSU based ion-conducting materials").
  • PPSU polyphenylsulfone
  • One preferred PPSU based ion-conducting material comprises repeating units of the formula
  • phenyl rings may be substituted or unsubstituted.
  • the PPSU based ion-conducting materials of the present invention have an IEC from at least about 0.5 meq./g to about 4 meq./g. In some embodiments, these materials further comprise sulfone crosslinkages and/or antioxidants.
  • PPSU based ion-conducting materials of the present invention may be used in the preparation of solid polymer electrolyte membranes.
  • Such solid polymer electrolyte membrane may contain sulfone crosslinkages.
  • One method of producing PPSU based ion-conducting materials of the present invention which are suitable for use in electrochemical applications comprises: providing a solution of a PPSU polymer; allowing the PPSU polymer to precipitate from the solution; adding a sulfonating agent comprising sulfur trioxide to the solution to form a sulfonated PPSU polymer, wherein the sulfur trioxide is diluted in solvent comprising a chlorinated hydrocarbon; and isolating the sulfonated PPSU polymer from the solution.
  • Methylene chloride is one preferred chlorinated hydrocarbon solvent for use in the present invention.
  • the method further comprises purifying the ion- conducting material to remove overly sulfonated or degraded fractions of the PPSU based ion-conducting material. This is accomplished in one preferred method by re-dissolving the sulfonated PPSU polymer in a solvent, and re- precipitating the sulfonated PPSU polymer into water, water saturated with sodium chloride, methanol or other non-solvent.
  • the method of forming PPSU based ion-conducting polymers of the present invention may further comprise crosslinking the ion-conducting material, especially when the ion-conducting material is in the H+ form.
  • the preferred methods may also comprise adding antioxidants to the sulfonated PPSU polymer, either before or following isolation of the sulfonated PPSU polymer.
  • Yet other preferred methods include halogenating, e.g., chlorinating or brominating PPSU based ion-conducting materials.
  • the present invention relates to novel ion-conducting materials which may be used to produce solid polymer electrolyte membranes (SPEMs). These materials could also be used in composite SPEMs comprising a substrate polymer and ion-conducting material component.
  • SPEMs solid polymer electrolyte membranes
  • novel ion-conducting materials and SPEMs of the present invention are designed to address the present shortcomings of today's leading solid polymer electrolyte membranes, e.g., Nafion® and other Naf ⁇ on®-like membranes, such as Gore-Select®.
  • Materials and membranes of the present invention may be used in a host of electrochemical applications, including but not limited to, polarity-based chemical separations; electrolysis; fuel cells and batteries; pervaporation; reverse osmosis - water purification, gas separation; dialysis separation; industrial electrochemistry, such as choralkali production and other electrochemical applications; water splitting and subsequent recovery of acids and bases from waste water solutions; use as a super acid catalyst; use as a medium in enzyme immobilization, for example; or use as an electrode separator in conventional batteries.
  • electrochemical applications including but not limited to, polarity-based chemical separations; electrolysis; fuel cells and batteries; pervaporation; reverse osmosis - water purification, gas separation; dialysis separation; industrial electrochemistry, such as choralkali production and other electrochemical applications; water splitting and subsequent recovery of acids and bases from waste water solutions; use as a super acid catalyst; use as a medium in enzyme immobilization, for example; or use as an electrode separator in conventional batteries.
  • Such processes generally comprise providing a solution of a polyaryletherketone (PEK) homopolymer, PEK copolymer or blends thereof, or a polyphenyl sulfone (PPSU) homopolymer, PPSU copolymer or blends thereof; adding a sulfonating agent to the polymer solution; and isolating the sulfonated polymer from the solution.
  • Post-processing steps i.e., purification, cross-linking, use of antioxidants, chlorination or bromination of the aromatic polymer backbone
  • the ion-conducting material comprises a sulfonated PEK homopolymer, PEK copolymer or a blend thereof.
  • PEK homopolymer has the repeating unit shown below:
  • the phenyl rings of the PEK homopolymer may be substituted or unsubstituted.
  • the PEK hompolymer, PEK copolymer or blends thereof be sulfonated in the absence of ether-phenyl-ether linkages (e.g., in the absence of PEKPEEK copolymerization).
  • PEK homopolymer e.g., available from Victrex USA
  • concentrated sulfuric acid e.g., available from Victrex USA
  • Slow addition of oleum reacts with the water present in the solution producing a more concentrated form of sulfuric acid solvent that eventually contains free SO 3 (after all the water has reacted).
  • Further addition of oleum increases the sulfonating power of the solution.
  • the water content is lowered, thereby increasing the sulfonating power of the solution.
  • Care must be taken to avoid excessive SO 3 content or overheating of the solution in order to minimize polymer degradation.
  • Overhead stirring of the solution and a room temperature water bath are highly recommended. Maintenance of the concentration of the reactant acid solution is critical. As these solutions are hygroscopic, they tend to change concentration due to moisture absorption with every exposure to air. Careful monitoring of their density can be used to check concentration. Titration may be used to monitor concentration.
  • the sulfonated PEK based ion-conducting product can be isolated by precipitation into water provided that the extent of sulfonation has not made it water soluble (methanol / water or water saturated with salt may also provide for a high degree of sulfonation). Longer reaction times or a larger excess of sulfur trioxide will cause more sulfonation.
  • Preferable temperature ranges for the reaction are as follows: 0-80°C including chilling the initial PEK polymer solution before, after, or during the addition of the oleum. However, since pure H 2 SO 4 solutions will freeze at approximately 10°C, it is preferable to maintain a temperature between 10-60°C.
  • reaction conditions include using a free SO 3 content of between about 0 (about 100% sulfuric acid) to about 30 wt.% (about 70% sulfuric acid).
  • Optimal content is dependent upon other reaction conditions (i.e., temperature), but generally SO 3 content is preferred to be between l-25wt.%.
  • the final concentration of polymer depends upon the starting sulfuric acid concentration, the free SO 3 level desired, and the concentration of fuming sulfuric acid added. Generally preferred concentration ranges include the following:
  • 10wt.% polymer ( ⁇ 5-30wt.%) in concentrated sulfuric acid (preferably 80-100%, more preferably 90-99%).
  • Oleum SO 3 /H 2 SO 4
  • a free SO 3 content is preferably between 10-60wt.%, more preferably approximately 20- 30wt.%.
  • pure SO 3 also may be used under the appropriate conditions.
  • reaction conditions may be tailored to produce sulfonated PEK based ion-conducting materials having IECs from at least about 0.5 to at least about 4 meq./g.
  • ion-conducting materials comprising sulfonated PEK homopolymers, copolymers or blends thereof, can be isolated via direct precipitation into water (or salt water) depending on the level of sulfonation.
  • sulfonated PEK may not be sufficient for long-term use in fuel cells, many electrochemical applications do not require hydrolytic stability at this level.
  • the ion- conducting material comprises at least one of a sulfonated PPSU homopolymer, PPSU copolymer or blends thereof.
  • This polymer has the repeating unit shown below:
  • the phenyl rings of the PPSU polymer may be substituted or unsubstituted.
  • controllable sulfonation of PPSU homopolymers, copolymers and blends thereof can be achieved using a methylene chloride (solvent)/ sulfur trioxide (sulfonating agent) system.
  • One preferred process of the present invention for preparing PPSU based ion-conducting materials is described as follows: the polymer is first dissolved in a suitable solvent, preferably methylene chloride or another non-reactive solvent, e.g., halogenated hydrocarbons or nitrobenzene and the like. The polymer solution is allowed to stir until the polymer precipitates and a slush-like suspension is formed. Sulfonation is performed by admixture of the PPSU polymer suspension and a sulfonating agent, preferably, sulfur trioxide. The amount of sulfonating agent added controls the degree of sulfonation. Preferably, temperatures are maintained between -10 to 25°C.
  • the methods for preparing PPSU based ion-conducting materials of the present invention may be further optimized by additional dilution of the polymer solution with solvent and extending the addition time of the sulfonating agent.
  • concentration ranges for the PPSU based ion- conducting materials of the present invention include the following: 5-30wt.%, preferably 10-20wt% (initial polymer solution, before dilution of any excess solvent).
  • This method can be used to produce highly sulfonated polymeric films (IEC of at least about 0.5 meq./g to at least about 4.0 meq./g), with equally high conductivity (IC of at least about 0.01 to about 0.5 S/cm) and minimal polymeric degradation.
  • IEC highly sulfonated polymeric films
  • IC electrical conductivity
  • heterogeneity of the sulfonated PPSU based ion-conducting polymers may result from the sulfonation procedure. Heterogeneity may not be severe enough to cause the polymer to precipitate during the sulfonation procedure, but some distribution may exist as the polymer crystallites sulfonate from the outside in. That is, some portions of the sulfonated polymer may be so highly sulfonated as to be water soluble (possibly leaching out during fuel cell operation) or otherwise degraded.
  • the purification procedure involves re-dissolving the ion-conducting polymer in a suitable solvent (e.g., NMP), and re-precipitating it into water or saturated NaCl solution. Re-precipitation of the ion-conducting polymer into saturated salt solution has been shown to result in a high yield of the ion- conducting polymer, while removing polymer that has been excessively sulfonated or degraded.
  • a suitable solvent e.g., NMP
  • the stability of the ion-conducting materials of the present invention may be enhanced by several post-processing steps. These steps include the following: (i) cross-linking the ion-conducting polymer in the H+ form to develop sulfone cross-links; (ii) addition of small amounts of antioxidants (insoluble) into the ion-conducting polymer; and (iii) chlorination / bromination of the ion-conducting polymer backbone, thereby reducing degradation sites.
  • Crosslinking methods can provide or enhance peroxide stability.
  • U.S. Patent No. 5,795,496 describes a method of crosslinking ion-conducting polymers via the SO 3 H groups (sulfonic acid groups) to form sulfone crosslinks between polymer chains.
  • This method entails sulfonating the polymer (e.g., PEEK) using concentrated sulfuric acid, casting of a film, then heating the film to a temperature of 120°C under vacuum. It is the heating step which causes the crosslinking to occur.
  • crosslinking procedure results in decreased ionic conductivity, water adsorbtion and swelling of the polymer.
  • adjustments can be made to the crosslinking procedures employed in order to minimize the sacrifice of ionic conductivity.
  • additives can also provide or enhance peroxide stability of the PEK and PPSU based ion-conducting materials of the present invention.
  • Polymer additives can be used as radical scavengers within the ion-conducting component of the ion-conducting material or SPEM. Examples of these include Irganox 1135 (Primary Phenolic Antioxidant, commercially available from Ciba Geigy) and DTTDP (Di(tridecyl) Thiodipropionate, Secondary Antioxidant, commercially available from Hampshire).
  • PEK and PPSU based ion-conducting materials of the present invention may be used to produce SPEMs using standard membrane casting techniques. Such techniques are well known to the skilled artisan.
  • films can be made by dissolving the polymer in a suitable solvent and casting onto a glass plate (or other surface). More specifically, the ion conducting polymer can be dissolved in n-methyl pyrrolidone (NMP), filtered, and then cast onto the substrate. The films are slowly evaporated in a low humidity chamber, then dried in a vacuum oven to fully densify. Once dry the films can be removed from the casting substrate by immersion in water.
  • NMP n-methyl pyrrolidone
  • the PEK and PPSU based ion-conducting materials and SPEMs of the present invention have limited methanol permeability (limited methanol diffusivity and solubility) even at elevated temperatures and pressures, are substantially chemically stable to acids and free radicals, and thennally/hydrolytically stable to temperatures of at least about 100°C.
  • the PEK and PPSU based ion-conducting membranes of the present invention have an ion-exchange capacity (IEC) of >1.0meq/g dry membrane (preferably, 1.5 to 2.0meq/g) and are highly ion-conducting (preferably, from about 0.01 to about 0.5S/cm, more preferably, to greater than about 0.1 S/cm or ⁇ 10 ⁇ cm resistivity).
  • IEC ion-exchange capacity
  • Ion-conducting materials and SPEMs of the present invention are durable, substantially defect-free, and dimensionally stable (less than about 20% change in dimension wet to dry), preferably even above temperatures of at least about 100°C.
  • Particularly preferred PEK and PPSU based ion-conducting materials have the ability to survive operation in fuel cells (i.e., H 2 /O 2 , methanol) for at least about 5000 hours (e.g., automotive applications).
  • fuel cells i.e., H 2 /O 2 , methanol
  • the PEK and PPSU based ion-conducting materials for use in the present invention may be substituted or unsubstituted. These materials may be present as homopolymers, copolymers, or other blends.
  • the class of PEK and PPSU homopolymers, copolymers, and blends thereof disclosed herein may include any desired substituents, provided that such substituents do not substantially impair properties desired for the intended use of the polymer, as may readily be determined by one of ordinary skill in the art. Such properties may include ionic conductivity, chemical and structural stability, swelling properties and so forth.
  • the utility of blending polymers to form a PEK and PPSU based ion- conducting material of the present invention is in optimizing each of their properties. Unlike simple mixing, blending does not create a composite material with two dispersed components. Rather, the blend is uniform in composition throughout. It may be useful to blend a sulfonated polymer with an unsulfonated one to optimize swelling, fuel crossover resistance, conductivity, peroxide resistance, hydrolytic stability and the like. Similarly, the blending of two sulfonated polymers might allow improved properties over each individual component. This concept may also be employed to improve the strength, cost, processability or stability of the ion-conducting materials of the present invention.
  • relatively low cost ion-conducting materials of the present invention may be produced which exhibit improved power density and reduced sensitivity to carbon monoxide in hydrogen fuel.
  • Ion-conducting materials of the present invention also alleviate water management problems which limit the efficiency of present Nafion® membrane- based fuel cells.
  • Ion-conducting materials of the present invention exhibit resistance to degradation and hydrolysis, as well as resistance to stress-induced creep. Ion-conducting materials of the present invention exhibit high ionic conductivity, high resistance to dehydration, high mechanical strength, chemical stability during oxidation and hydrolysis, low gas permeability to limit parasitic losses, and stability at elevated temperatures and pressures.
  • Ion-conducting materials of the present invention are resistant to methanol crossover when used in a direct methanol fuel cell. This results in high efficiency and improved cell performance.
  • Ion-conducting materials of the present invention utilize relatively low cost starting materials and fabrication methods, and therefore can be produced at a fraction of the cost of those membranes employing Nafion® and Nafion®-like ionomers.
  • Ion-conducting materials of the present invention of the present invention act as a barrier against reactants (H 2 , O 2 and methanol permeation) in fuel cell applications.
  • Surfactants or surface active agents having a hydrophobic portion and hydrophilic portion may be utilized in producing ion-conducting materials of the present invention of the present invention. These agents are well known in the art and include Triton X-100 (commercially available from Rohm & Haas of Philadelphia, PA).
  • Compatibilizers may also be employed in producing membranes of the present invention.
  • "compatibilizers” refer to agents that aid in the blendability of two or more polymers that would otherwise be resistant to such blending. Examples include block copolymers containing connecting segments of each component.
  • the PEK and PPSU based ion-conducting materials, SPEMs and methods of the present invention will be further illustrated by the Table and Examples below.
  • Boil deionized water in separate beakers on hotplate. 4. Place films into boiling water.
  • Ion-conducting polymeric samples can be crosslinked in the acid (H+) form to improve ICP stability. Normally, crosslinking is performed in vacuum, to exclude oxygen from the system (which can cause ICP charring). The vacuum oven should be preheated to temperatures of at least about 200°C. The ICP sample is then heated in the vacuum oven for a prolonged period of time. The ICP sample should be tested before and after crosslinking for IEC and peroxide stability in order to evaluate long term membrane stability. See e.g., Example 5 below.
  • Ion-conducting materials of the present invention may be used to produce
  • films can be made by dissolving the polymer in a suitable solvent and casting onto a glass plate (or other surface).
  • the ion conducting polymer can be dissolved in n-methyl py ⁇ olidone (NMP), filtered, and then cast onto the substrate.
  • NMP n-methyl py ⁇ olidone
  • the films are slowly evaporated in a low humidity chamber, then dried in a vacuum oven to fully densify. Once dry the films can be removed from the casting substrate by immersion in water.
  • Aromatic PES polymers can be sulfonated to controlled degrees of substitution with sulfonating agents. The degree of substitution is controlled by the choice of and mole ratio of sulfonating agent to aromatic rings of the polymer, by the reaction temperature and by the time of the reaction. This procedure offers a method for carrying out sulfonation in a heterogeneous manner, i.e., sulfonation of precipitated polymer crystals.
  • the polymer preferably a polyethersulfone
  • the appropriate solvent preferably methylene chloride
  • Sulfonation is carried out by simple admixture of the suspension with a sulfonating agent. Suitable agents include chorosulfonic acid and, preferably, sulfur trioxide (Allied chemicals stabilized Sulfan B® in CH 2 C1 2 ).
  • the sulfonating agent used should be in sufficient proportion to introduce a number of sulfonate groups onto the polymer that is within the range of between 0.4: 1 to 5: 1 per polymer repeat unit, although this is not critical.
  • the temperature at which sulfonation takes place is critical to limiting the side reactions but varies with the type of polymer (a preferable temperature is within the range of from -50° to 80°C, preferably -10° to +25°C).
  • the sulfonated polymer may be separated from the reaction mixture by conventional techniques such as by filtration, washing and drying.
  • the polymer products of the process of the invention may be neutralized with the addition of a base, such as sodium bicarbonate, when desired and converted to the alkali salts thereof.
  • a base such as sodium bicarbonate
  • the alkali salts of the polymer products of the invention may be used for the same purposes as the parent acid polymers.
  • Concentrated sulfuric acid is used as the solvent in this procedure.
  • the content of the sulfonating agent, sulfur trioxide is based on the total amount of pure (100%) anhydrous) sulfuric acid present in the reaction mixture, and is kept to a value of less than 6% by weight throughout the entire sulfonation.
  • the sulfur trioxide may be mixed in dissolved form (oleum, fuming sulfuric acid) with concentrated sulfuric acid. The concentration of the starting sulfuric acid and oleum were determined by measuring their density immediately before use in the reactions.
  • the temperature of the reaction mixture is kept at less than +30°C throughout the reaction.
  • the sulfonation procedure is stopped with the addition of water to the reaction mixture or by pouring the reaction mixture into water.
  • the polymer is first dried in high vacuum at room temperature to constant weight, then dissolved in concentrated sulfuric acid.
  • Oleum is then added drop-wise over a period of hours with constant cooling below +30°C, and with stirring. When all of the oleum has been added, the reaction mixture is stirred for a further period of hours at the same temperature.
  • the resultant viscous solution is then run into water and the precipitated polymer is filtered off.
  • the polymer is then washed with water until the washings no longer are acidic, and it is then dried.
  • films are immersed in distilled H 2 O and boiled for a period of 30 minutes.
  • the films are then placed in a solution of 1.5N H 2 SO 4 at room temperature and soaked for a period of 30 minutes. This is repeated three separate times to ensure proper H+ ion exchange into the membrane.
  • Films are rinsed free of acid (pH of rinse water > 5.0) and placed into separate beakers, each filled with a saturated solution of NaCl.
  • the salt solution is boiled for a period of three hours.
  • the films, which are now in the Na+ form are removed from the salt solution, rinsed with distilled water and padded to remove excess water. Now a wet weight and thickness of the sample are measured.
  • the films While in the Na+ form, the films are dried in an air oven at a temperature of 60°C. The dry weight and thickness of the films are measured and the percent water content is calculated. The salt solutions are titrated with 0.1N NaOH to a phenolphthalein endpoint and IEC dry (meq/g) values calculated.
  • Transverse ionic conductivity measurements are performed on film samples in order to determine the specific resistance (ohm*cm 2 ).
  • film samples Prior to the ionic conductivity measurements, film samples are exchanged into the H+ form using the standard procedure discussed above. To measure the ionic conductivity, the film samples are placed in a die consisting of platinum-plated niobium plates. The sample size tested is 25cm 2 .
  • Measurements are converted to specific resistance by calculating the ratio of thickness over conductivity (ohm*cm2).
  • Accelerated degradation testing is carried out using 3% H 2 O 2 solution with 4 ppm Fe++ added as an accelerator.
  • the films are tested for a period of 8 hours at a temperature of 68°C.
  • the percent degradation of IEC was measured in the film samples after the test. After 8 hours, the films are removed from solution, and re- exchanged using 1.5 N H 2 SO 4 .
  • the IEC is recalculated, and the test result expressed as the % loss in IEC. This test simulates long term (several thousand hours) of actual fuel cell operation. For H 2 O 2 , fuel cells, ⁇ 10% IEC degradation in this test would be considered acceptable.
  • reaction mixtures were permitted to stir at ice bath temperatures for another 2.5 hours, then the reaction was stopped by adding approximately 10 ml of deionized water to each of the reaction mixtures.
  • reaction mixtures (white dispersions) were recovered by filtration using a glass frit.
  • Products (white powder) were washed 3X with 100 ml portions of dichloromethane. The washed products were then permitted to air dry in the hood. 20%) solutions of the dried products were made in NMP and cast on soda lime glass plates. The freshly cast films were left to stand in a dry box with a relative humidity of less than 5% for a period of 24 hours. The cast films were heated at 70°C under full dynamic vacuum for an hour prior to floating the films off with deionized water. The floated films were then permitted to air dry overnight.
  • the 100% and 150% sulfonated products swell greatly in water and become opaque, but when films are dry they shrink and become clear once again.
  • the mechanical strength of these films allows creasing while resisting tearing.
  • Films of the 100% and 150% products are not soluble in boiling water, and under these conditions also maintain their mechanical properties.
  • the sulfonated polymers were dried overnight, dissolved in NMP (at 20wt.%) and then precipitated into a large excess of distilled water, followed by soaking in sodium bicarbonate solution (to convert to the sodium salt form).
  • sample B was added to approximately 4 liters of acetone.
  • the acetone caused the collapse of the water swollen polymer which was then isolated by filtration. It also caused a significant portion to dissolve, which was isolated by drying of the acetone / water mixture (Sample B-l).
  • Samples B and B-l contained approximately the same amount of polymer, but showed varying properties. In particular, the sulfonated polymer that was not extracted into acetone showed a slightly lower IEC, and a significantly lower water up-take.
  • PEK polymer 30.00g was dissolved in 270g of concentrated sulfuric acid (93.5wt.%>) under nitrogen, sti ⁇ ed by an overhead mechanical sti ⁇ er. The polymer was dispersed over several days to form a dark red thick solution.
  • the 1 and 3 hour products were washed several times with deionized water, soaked overnight in approximately 0.5M NaOH solution, then washed until a neutral pH was achieved. These were blotted dry and placed in the vacuum oven overnight at 50°C. Dried samples were dissolved in NMP to make a 20wt. % solution. This required heating overnight at 60°C. Films of approx. 6 mils were cast onto a freshly cleaned glass plate. After two days of drying the films were removed by immersion into deionized water.
  • Ion-conducting polymeric samples can be crosslinked in the acid (H+) form to improve ICP stability. Normally, crosslinking is performed in vacuum, to exclude oxygen from the system (can cause ICP charring).
  • SPPSU was crosslinked in a vacuum oven preheated to temperatures of 200, 225 and 250°C for durations of up to 8 hours. Under these conditions, samples showed a slight IEC loss ( ⁇ 10%>), and little improvement in long term stability (peroxide test). More severe conditions were employed by exposing samples to 250°C in full vacuum for more than 20 hours. Peroxide testing did not show any considerable difference between SPPSU crosslinked films and SPPSU controls until heated for at least 32 hours.
  • the SPPSU films crosslinked at 250°C for 32 hours and 72 hours maintained their film integrity during the peroxide accelerated life test.
  • the IEC of these test samples decreased significantly. Specifically, a loss of 63%o (1.90 to 0.69 meg/g) for the 32 hour sample and a loss of 73% (1.90 meg/g to 0.51 meq./g) for the 72 hour crosslinked SPPSU films was calculated. It is anticipated that many of the SO 3 H acid groups form aromatic sulfone (Ar- SO 2 -Ar) crosslinks between polymer chains. This trend confirms that crosslinking (H+ form) of sulfonated polymers can be used to improve long term membrane stability.

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  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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Abstract

La présente invention concerne des matériaux conducteurs d'ions convenant comme membranes d'électrolytes polymères pour l'électrochimie et notamment les piles à combustible. L'invention concerne plus particulièrement des matériaux conducteurs d'ions à base de polymères de polyaryléthercétones ou de polyphénylsulfones sulfonés, y-compris de certains de leurs copolymères et de leurs mélanges. L'invention concerne également la production de tels matériaux conducteurs d'ions.
PCT/US1999/019470 1998-08-28 1999-08-26 Materiaux conducteurs d'ions pour l'electrochimie et procedes correspondants WO2000024796A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP99965719A EP1115769A1 (fr) 1998-08-28 1999-08-26 Materiaux conducteurs d'ions pour l'electrochimie et procedes correspondants
CA002342221A CA2342221A1 (fr) 1998-08-28 1999-08-26 Materiaux conducteurs d'ions pour l'electrochimie et procedes correspondants
JP2000578363A JP2003503510A (ja) 1998-08-28 1999-08-26 電気化学的用途での使用に好適な新規なイオン伝導性材料およびそれに関連する方法
AU21424/00A AU2142400A (en) 1998-08-28 1999-08-26 Novel ion-conducting materials suitable for use in electrochemical applications and methods related thereto

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PCT/US1998/017898 WO1999010165A1 (fr) 1997-08-29 1998-08-28 Membranes composites d'electrolytes a polymeres solides
USPCT/US98/17898 1998-08-28
US26286199A 1999-03-03 1999-03-03
US09/262,861 1999-03-03

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WO2000024796A1 true WO2000024796A1 (fr) 2000-05-04
WO2000024796A8 WO2000024796A8 (fr) 2000-09-14

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JP (1) JP2003503510A (fr)
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WO (1) WO2000024796A1 (fr)

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JP2003201352A (ja) * 2002-01-08 2003-07-18 Honda Motor Co Ltd 高分子電解質膜、該高分子電解質膜を備える膜電極構造体及び該膜電極構造体を備える固体高分子型燃料電池
WO2005068536A1 (fr) * 2004-01-13 2005-07-28 Johnson Matthey Public Limited Company Polymeres conducteurs d'ions et membranes les composant
EP1680821A2 (fr) * 2003-08-28 2006-07-19 Hoku Scientific, Inc. Electrolyte composite dote d'agents de reticulation
EP1772922A1 (fr) * 2005-10-06 2007-04-11 Samsung SDI Co., Ltd. Couche catalytique pour une assemblage membrane-électrode d'une pile à combustible, composé pour la formation de la couche catalytique, procédé de preparation la couche catalytique, et assemblage membrane-électrode comprenant la couche catalytique
WO2007075540A2 (fr) * 2005-12-20 2007-07-05 General Electric Company Copolymeres sequences de polyarylethercetone-polyethersulfone sulfonees
WO2008005647A2 (fr) * 2006-07-03 2008-01-10 General Electric Company Copolymères blocs de polyaryléthercétone sulfonée et de polyéthersulfone.
WO2010072715A1 (fr) * 2008-12-23 2010-07-01 Basf Se Batteries à couche mince non rechargeables présentant des polymères à fonctionnalisation anionique en tant que séparateurs
US7754844B2 (en) 2002-10-08 2010-07-13 Toyo Boseki Kabushiki Kaisha Polyarylene ether compound containing sulfonic acid group, composition containing same, and method for manufacturing those
US7799485B2 (en) 2004-07-09 2010-09-21 Nissan Motor Co., Ltd. Fuel cell system and composition for electrode
US7833676B2 (en) 2004-07-09 2010-11-16 Nissan Motor Co., Ltd. Fuel cell system and solid polymer electrolyte film
US7910248B2 (en) * 2003-04-28 2011-03-22 Sumitomo Chemical Company, Limited Aromatic-polyether-type ion-conductive ultrahigh molecular weight polymer, intermediate therefor, and process for producing these
US8216727B2 (en) 2004-11-10 2012-07-10 Toyo Boseki Kabushiki Kaisha Aromatic hydrocarbon based proton exchange membrane and direct methanol fuel cell using same
US9112196B2 (en) 2005-12-15 2015-08-18 Nissan Motor Co., Ltd. Fuel, fuel cell system, fuel cell vehicle and operating method for fuel cell system
EP3340350A4 (fr) * 2015-08-17 2019-04-17 National Institute for Materials Science Électrolyte polymère conducteur de protons à base de polyphénylsulfone, membrane d'électrolyte polymère solide conducteur de protons, couche catalytique d'électrode pour cellules à combustible polymères solides, procédé de fabrication d'une couche catalytique d'électrode pour cellules à combustible polymères solides, et cellule à combustible

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JP3412763B2 (ja) * 2001-01-19 2003-06-03 本田技研工業株式会社 複合高分子電解質膜及びそれを用いた固体高分子型燃料電池
JP4590824B2 (ja) * 2003-02-10 2010-12-01 東洋紡績株式会社 スルホン化芳香族ポリエーテル系化合物、その複合体、およびそれらの製造方法。
JP2005203195A (ja) * 2004-01-14 2005-07-28 Hitachi Cable Ltd 燃料電池用電解質膜及びその製造方法、燃料電池及びその製造方法、固体高分子膜電極アセンブリ
JP4830357B2 (ja) * 2004-09-06 2011-12-07 日産自動車株式会社 固体高分子型燃料電池システム及び燃料電池車両
JP4876407B2 (ja) * 2005-02-28 2012-02-15 日産自動車株式会社 固体高分子型燃料電池用電解質、固体高分子型燃料電池、固体高分子型燃料電池システム及び燃料電池車両
JP4876389B2 (ja) * 2004-07-09 2012-02-15 日産自動車株式会社 固体高分子型燃料電池用電解質、固体高分子型燃料電池、固体高分子型燃料電池システム及び燃料電池車両
JP4910310B2 (ja) * 2004-07-09 2012-04-04 日産自動車株式会社 電極用組成物、電極、空気極用組成物、燃料電池用空気極、燃料電池、燃料電池システム及び燃料電池車両
JP5023475B2 (ja) * 2004-12-14 2012-09-12 日産自動車株式会社 電極システム、燃料電池、燃料電池システム、家電機器、携帯機器及び輸送用機器
JP5118803B2 (ja) * 2005-03-02 2013-01-16 株式会社豊田中央研究所 燃料電池システム及び固体高分子型燃料電池の運転方法
JP5442925B2 (ja) * 2006-04-28 2014-03-19 一般財団法人電力中央研究所 ポリ塩化ビフェニル類の分析方法
CN105879696A (zh) * 2014-12-16 2016-08-24 天津工业大学 一种高亲水性内压式聚砜/磺化聚砜中空纤维超滤膜及其制备方法
CN111916628A (zh) * 2020-07-14 2020-11-10 盐山万兴新能源有限公司 一种锂离子电池隔膜及其制备方法

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US5438082A (en) * 1992-06-13 1995-08-01 Hoechst Aktiengesellschaft Polymer electrolyte membrane, and process for the production thereof
US5561202A (en) * 1992-06-13 1996-10-01 Hoechst Aktiengesellschaft Polymer electrolyte membrane, and process for the production thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003201352A (ja) * 2002-01-08 2003-07-18 Honda Motor Co Ltd 高分子電解質膜、該高分子電解質膜を備える膜電極構造体及び該膜電極構造体を備える固体高分子型燃料電池
US7754844B2 (en) 2002-10-08 2010-07-13 Toyo Boseki Kabushiki Kaisha Polyarylene ether compound containing sulfonic acid group, composition containing same, and method for manufacturing those
US7910248B2 (en) * 2003-04-28 2011-03-22 Sumitomo Chemical Company, Limited Aromatic-polyether-type ion-conductive ultrahigh molecular weight polymer, intermediate therefor, and process for producing these
EP1680821A4 (fr) * 2003-08-28 2008-03-26 Hoku Scient Inc Electrolyte composite dote d'agents de reticulation
EP1680821A2 (fr) * 2003-08-28 2006-07-19 Hoku Scientific, Inc. Electrolyte composite dote d'agents de reticulation
US7736539B2 (en) 2004-01-13 2010-06-15 Johnson Matthey Public Limited Company Ion-conducting polymers and membranes comprising them
WO2005068536A1 (fr) * 2004-01-13 2005-07-28 Johnson Matthey Public Limited Company Polymeres conducteurs d'ions et membranes les composant
US8252481B2 (en) 2004-07-09 2012-08-28 Nissan Motor Co., Ltd. Fuel cell system and solid polymer electrolyte film
US7833676B2 (en) 2004-07-09 2010-11-16 Nissan Motor Co., Ltd. Fuel cell system and solid polymer electrolyte film
US7799485B2 (en) 2004-07-09 2010-09-21 Nissan Motor Co., Ltd. Fuel cell system and composition for electrode
US8216727B2 (en) 2004-11-10 2012-07-10 Toyo Boseki Kabushiki Kaisha Aromatic hydrocarbon based proton exchange membrane and direct methanol fuel cell using same
EP1772922A1 (fr) * 2005-10-06 2007-04-11 Samsung SDI Co., Ltd. Couche catalytique pour une assemblage membrane-électrode d'une pile à combustible, composé pour la formation de la couche catalytique, procédé de preparation la couche catalytique, et assemblage membrane-électrode comprenant la couche catalytique
US8173323B2 (en) 2005-10-06 2012-05-08 Samsung Sdi Co., Ltd. Binder for a fuel cell catalyst composition, a membrane electrode assembly for a fuel cell using the binder and a method for preparing a membrane electrode assembly
US9112196B2 (en) 2005-12-15 2015-08-18 Nissan Motor Co., Ltd. Fuel, fuel cell system, fuel cell vehicle and operating method for fuel cell system
US7595373B2 (en) 2005-12-20 2009-09-29 General Electric Company Sulfonated polyaryletherketone-polyethersulfone block copolymers
WO2007075540A2 (fr) * 2005-12-20 2007-07-05 General Electric Company Copolymeres sequences de polyarylethercetone-polyethersulfone sulfonees
WO2007075540A3 (fr) * 2005-12-20 2007-08-16 Gen Electric Copolymeres sequences de polyarylethercetone-polyethersulfone sulfonees
WO2008005647A3 (fr) * 2006-07-03 2008-03-06 Gen Electric Copolymères blocs de polyaryléthercétone sulfonée et de polyéthersulfone.
WO2008005647A2 (fr) * 2006-07-03 2008-01-10 General Electric Company Copolymères blocs de polyaryléthercétone sulfonée et de polyéthersulfone.
WO2010072715A1 (fr) * 2008-12-23 2010-07-01 Basf Se Batteries à couche mince non rechargeables présentant des polymères à fonctionnalisation anionique en tant que séparateurs
EP3340350A4 (fr) * 2015-08-17 2019-04-17 National Institute for Materials Science Électrolyte polymère conducteur de protons à base de polyphénylsulfone, membrane d'électrolyte polymère solide conducteur de protons, couche catalytique d'électrode pour cellules à combustible polymères solides, procédé de fabrication d'une couche catalytique d'électrode pour cellules à combustible polymères solides, et cellule à combustible
US10862151B2 (en) 2015-08-17 2020-12-08 National Institute For Materials Science Polyphenylsulfone-based proton conducting polymer electrolyte, proton conducting solid polymer electrolyte membrane, electrode catalyst layer for solid polymer fuel cells, method for producing electrode catalyst layer for slid polymer fuel cells, and fuel cell

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CA2342221A1 (fr) 2000-05-04
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EP1115769A1 (fr) 2001-07-18
JP2003503510A (ja) 2003-01-28

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