WO2024206331A1 - Polymères de fluorure de sulfonyle fluorés composés et membranes échangeuses d'ions fabriquées à partir de ceux-ci - Google Patents

Polymères de fluorure de sulfonyle fluorés composés et membranes échangeuses d'ions fabriquées à partir de ceux-ci Download PDF

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WO2024206331A1
WO2024206331A1 PCT/US2024/021511 US2024021511W WO2024206331A1 WO 2024206331 A1 WO2024206331 A1 WO 2024206331A1 US 2024021511 W US2024021511 W US 2024021511W WO 2024206331 A1 WO2024206331 A1 WO 2024206331A1
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precious metal
cation exchange
exchange membrane
metal catalyst
composition
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Todd S. Sayler
Erin S. FARRELL
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Chemours Co FC LLC
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Chemours Co FC LLC
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Priority to JP2025554908A priority Critical patent/JP2026513171A/ja
Priority to KR1020257035133A priority patent/KR20250169563A/ko
Priority to AU2024247425A priority patent/AU2024247425A1/en
Priority to EP24719426.9A priority patent/EP4689235A1/fr
Priority to CN202480018357.4A priority patent/CN120898031A/zh
Publication of WO2024206331A1 publication Critical patent/WO2024206331A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • B01D69/1213—Laminated layers
    • 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
    • B01D69/145—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
    • C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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

Definitions

  • the present invention describes compounded fluorinated sulfonyl fluoride polymers, ion exchange membrane precursors, ion exchange membranes, and the processes of making such materials.
  • the compounded polymers and ion exchange membranes have improved gas recombination catalyst dispersed throughout the resin and can be used to form electrolytic systems, including catalyst coated membranes, fuel cells, and water electrolysis systems.
  • Precious metal compounds can be added into electrolytic systems as a gas recombination catalyst (GRC) to help reduce hydrogen (H2) in oxygen that crosses through the cation exchange membrane during operation.
  • GRC gas recombination catalyst
  • H2 hydrogen
  • a key goal is to optimize the reduction in hydrogen crossover while minimizing the amount of precious metal compound used.
  • the present invention provides a novel way to strategically place a GRC in an extruded cation exchange membrane via processing methods.
  • One discovery of the invention is that strategic placement of the GRC provides a performance advantage, product configuration advantage, optimizes polymer entanglement and membrane swelling, limits the amount of raw materials required, and reduces the post-processing steps to incorporate a GRC.
  • the present invention describes compounded fluorinated sulfonyl fluoride polymers, ion exchange membrane precursors, ion exchange membranes, and the processes of making such materials.
  • the compounded polymers and ion exchange membranes have improved dispersion of gas recombination precious metal catalysts throughout the resin and can be used to form electrolytic systems, including catalyst coated membranes, fuel cells, and water electrolysis systems.
  • the present invention relates to a composition
  • a composition comprising about 90% to about 99.99% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalyst, based on the total weight of the composition, where the one or more precious metal catalyst is uniformly distributed throughout the one or more noncrosslinked fluorinated sulfonyl fluoride polymer.
  • the present invention also relates to a cation exchange membrane precursor comprising at least one proton exchange precursor layer, where the at least one proton exchange precursor layer comprises about 90% to about 99.99% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalysts, based on the total weight of the composition, where the one or more precious metal catalyst is uniformly distributed throughout the at least one proton exchange precursor layer.
  • the present invention further relates to A cation exchange membrane comprising at least one cation exchange layer, where the at least one proton exchange layer comprises about 90% to about 99.99% by weight of one or more non-crosslinked fluorinated sulfonic acid polymers and about 0.01 % to about 10% by weight of one or more precious metal catalysts, based on the total weight of the composition, where the one or more precious metal catalyst is uniformly distributed throughout the at least one cation exchange layer.
  • the present invention relates to A method of making a solid composition
  • a method of making a solid composition comprising: a. melting at least one non-crosslinked fluorinated sulfonyl fluoride polymer; b. uniformly distributing at least one precious metal catalyst in the at least one molten non-crosslinked fluorinated sulfonyl fluoride polymer in an amount to form a composition comprising about 90% to about 99.99% by weight of one or more non- crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalysts, based on the total weight of the composition; and c. cooling the mixture of step b to form a solid composition.
  • the present invention relates to a method of making a cation exchange membrane comprising: d. melting at least one non-crosslinked fluorinated sulfonyl fluoride polymer; e. uniformly distributing at least one precious metal catalyst with the at least one molten non-crosslinked fluorinated sulfonyl fluoride polymer in an amount to form a composition comprising about 90% to about 99.99% by weight of one or more non- crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalysts, based on the total weight of the composition; f.
  • a cathode exchange membrane made by the above method is also envisioned.
  • FIG. 1 is a scanning electron micrograph (SEM) image of Example 6.
  • FIG. 2 is an SEM image of Example 8.
  • FIG. 3 is an SEM image of Example 9.
  • FIG. 4 is an SEM image of Example 9 showing the thickness of the precious metal catalyst layer.
  • FIG. 5 is an SEM image of Example 17.
  • FIG. 6 is an SEM image of Example 18.
  • FIG. 7 is am SEM image of Comparative Example A.
  • uniformly distributed refers to precious metal catalyst being distributed uniformly throughout the volume in all three dimensions.
  • the process of uniformly distributing refers to distributing the material (or rather, redistributing the material) uniformly throughout three dimensions.
  • uniformly dispersed refers to precious metal catalyst being in a de-agglomerated form, such as discrete particles.
  • the process of uniformly dispersing refers to reducing the particle size of the original material by deagglomerating the original particle into a smaller particle, for example, a primary particle with higher surface area.
  • non-crosslinked fluorinated sulfonyl fluoride polymer refers to fluorinated sulfonyl fluoride polymers having no intentional crosslinkable monomers or repeat units and no added crosslinking agents.
  • non-crosslinked fluorinated sulfonic acid refers to fluorinated sulfonic acid polymers having no intentional crosslinkable monomers or repeat units, no added crosslinking agents, and where the sulfonic acid units are not bonded to other polymer units.
  • IXR ion exchange ratio
  • a cation exchange membrane precursor refers to a film that is capable of being converted into a cation exchange membrane by hydrolysis and optional acidification.
  • the cation exchange membrane precursor is a film comprising a fluorinated sulfonyl fluoride polymer.
  • a cation exchange resin precursor is a polymer or resin that is capable of being converted into a cation exchange polymer by hydrolysis and optional acidification.
  • the present invention relates to a composition
  • a composition comprising about 90% to about 99.99% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalyst, based on the total weight of the composition, where the one or more precious metal catalyst is uniformly distributed throughout the one or more noncrosslinked fluorinated sulfonyl fluoride polymer.
  • the precious metal catalyst can be any precious metal catalyst typically found in electrolytic cell applications.
  • the precious metal may be, but is not limited to, platinum, ruthenium, osmium, rhodium, iridium, palladium, or mixtures thereof.
  • the precious metal may also be mixed with additional compounds, as long as the precious metal content meets the range of about 0.01-10% by weight of the total composition.
  • the precious metal catalyst may be unsupported, or it may be supported by an inorganic support. Inorganic supports may be in any form, such as an inorganic support particle.
  • Inorganic materials composing the inorganic supports may be any suitable material, including but not limited to, carbon or inorganic materials such as those cited in US20080161429 or EP1929574, which are hereby incorporated by reference; or mixtures thereof.
  • Precious metal catalysts may have a high surface area to increase effectiveness, such that they have a precious metal surface area of at least 10 m 2 /g; in another aspect, at least 30 m 2 /g; and in another aspect, at least 45 m 2 /g.
  • the precious metal catalyst has an average particle size D50 less than about 5 pm; in another aspect, about 75 nm; in another aspect, an average particle size D50 less than about 50 nm; and in another aspect, an average particle size D50 less than about 25 nm.
  • Ion exchange membranes can be made of various ion exchange polymers.
  • Preferred ion exchange polymers, fluorinated sulfonic acids and fluorinated sulfonate salts can be made by hydrolyzing and then optionally protonating fluorinated sulfonyl fluoride polymers.
  • the fluorinated sulfonic acids, fluorinated sulfonate salts, and fluorinated sulfonyl fluoride polymers may or may not be chemically stabilized by fluorinating the polymer endgroups.
  • Suitable fluorinated sulfonyl fluoride polymers include at least one fluorinated sulfonyl fluoride repeat unit and optionally one or more repeat units, resulting from the free radical polymerization of at least one fluorinated sulfonyl fluoride monomer and optionally one or more monomers.
  • the fluorinated ionomer may contain the repeat unit:
  • the sulfonyl fluoride polymer is a copolymer made from two or more monomers.
  • suitable comonomers include, but are not limited to, tetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and mixtures thereof.
  • it may be a copolymer of a sulfonyl fluoride-containing monomer with TFE, resulting in a repeat unit -[CF2-CF2]-, or with other comonomers.
  • Monomers having pendant phosphonic acid groups may also be incorporated into the fluorinated sulfonyl fluoride polymer to yield, after conversion, a fluorinated ionomer containing both sulfonic acid groups and phosphonic acid groups.
  • These polymers are converted to sulfonates or sulfonic acids, for example, polymers disclosed in U.S. Patent No. 3,282,875, in U.S. Patent No. 4,358,545, or in U.S. Patent No. 4,940,525.
  • One preferred fluorinated sulfonyl fluoride polymer includes a perfluorocarbon backbone and a side chain represented by the formula -O- CF2CF(CF3)-O-CF2CF2SO2F. Fluorinated ionomers containing sulfonate or sulfonic acid groups of this type are disclosed in U.S. Patent No.
  • TFE tetrafluoroethylene
  • PSEPVE perfluoro(3,6 dioxa-4 methyl 7 octenesulfonyl fluoride)
  • PSEPVE also called long side-chain or LSC
  • Another preferred fluorinated sulfonyl fluoride polymer is of the type disclosed in U.S. Patent No. 4,358,545 and U.S.
  • PFSVE perfluoro(3 oxa-4- pentenesulfonyl fluoride)
  • a fluorinated sulfonate or sulfonic acid polymer is formed.
  • sulfonate or sulfonic acid groups refers to either sulfonic acid groups or salts of sulfonic acid, preferably alkali metal or ammonium salts.
  • Preferred functional groups are represented by the formula -SO3X wherein X is H, Li, Na, K or N(R 1 )(R 2 )(R 3 )(R 4 ), where R 1 , R 2 , R 3 , and R 4 are the same or different and are H, CH3, or C2H5.
  • the fluorinated sulfonate or sulfonic acid polymer is of the type available under the trade name of NafionTM (The Chemours Company FC, LLC, Wilmington, DE).
  • the fluorinated ionomer may contain the repeat unit: -[CF2-CF((CF2)b-(O-(CF2CFRf)c)a-O-(CF 2 CFR'f)dSO3X)]- where b is 0 or 1 ; c is an integer from 1 to 8; a is 0, 1 , or 2; d is an integer from 1 to 8; Rf and R'f are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms; and X is H, Li, Na, K or N(R 1 )(R 2 )(R 3 )(R 4 ) where R 1 , R 2 , R 3 , and R 4 are the same or different and are H, CH3 or C2H5.
  • segment ((CF2)b-(O-(CF2CFRf) c ) a -O-(CF2CFR'f)dSO3X) in the structure above is the pendant chain from the perfluorinated polymer backbone. Branched pendant chains having multiple sulfonic acid groups are also encompassed.
  • the fluorinated sulfonyl fluoride polymer has an ion exchange ratio of less than about 13.2.
  • ion exchange ratio refers to the number of carbon atoms in the polymer backbone in relation to the number of sulfonyl fluoride groups.
  • the fluorinated sulfonyl fluoride polymer has an IXR less than about 13.2; in another aspect, less than about 12.7; in another aspect, less than about 12.1 ; and in another aspect, less than about 11 .7; or any value, range, or sub-range therebetween.
  • the fluorinated sulfonyl fluoride polymer has an IXR of at least 7.1 ; in another aspect, at least 8.1 ; in another aspect, at least 9.1 ; and in another aspect, at least 10.1 ; or any value, range, or sub-range therebetween.
  • the fluorinated sulfonyl fluoride polymer and corresponding fluorinated sulfonate or sulfonic acid polymer has an equivalent weight (EW) less than about 1000; alternatively, less than about 980; alternatively less than about 950; alternatively less than about 930, or any value, range, or subrange therebetween.
  • the corresponding fluorinated sulfonate or sulfonic acid polymer has an EW of at least about 530; alternatively, at least about 580; alternatively, at least about 630; alternatively at least about 680, or any value, range, or sub-range therebetween.
  • EW refers to the weight of the corresponding fluorinated sulfonic acid polymer in proton form required to neutralize one equivalent of NaOH.
  • the fluorinated sulfonyl fluoride polymer and its corresponding fluorinated sulfonate or sulfonic acid polymer contains the long side chain and has an EW less than about 1000; alternatively less than about 980; alternatively less than about 950; alternatively less than about 930, or any value, range, or sub-range therebetween.
  • the fluorinated sulfonyl fluoride polymer and its corresponding fluorinated sulfonate or sulfonic acid polymer has an EW of at least about 700; alternatively, at least about 750; alternatively, at least about 800; alternatively at least about 950, or any value, range, or sub-range therebetween.
  • the fluorinated sulfonyl fluoride polymer and its corresponding fluorinated sulfonate or sulfonic acid polymer contains the short side chain and has an EW less than about 840; alternatively less than about 810; alternatively less than about 785; alternatively less than about 765, or any value, range, or sub-range therebetween.
  • the fluorinated sulfonyl fluoride polymer and its corresponding fluorinated sulfonate or sulfonic acid polymer has an EW of at least about 530; alternatively, at least about 580; alternatively, at least about 630; alternatively at least about 680, or any value, range, or sub-range therebetween.
  • the precious metal catalyst is specifically combined with the fluorinated sulfonyl fluoride version of the polymer, rather than the corresponding fluorinated sulfonate or fluorinated sulfonic acid. It is believed that blending the precious metal catalyst directly into the fluorinated sulfonyl fluoride will allow more uniformly distributed and more uniformly dispersed catalyst throughout the polymer, leading to a more uniformly distributed or more uniformly dispersed catalyst in materials made from the composition, such as fluorinated sulfonyl fluoride films, corresponding fluorinated sulfonate polymer materials, corresponding fluorinated sulfonic acid polymer materials, and films or membranes thereof. In one aspect, the precious metal catalyst is uniformly dispersed throughout the composition.
  • the precious metal catalyst is present in the composition in an amount sufficient to provide gas recombination effects, but not so much as to alter the electrical conductivity (or lack thereof) of the non-crosslinked fluorinated sulfonyl fluoride polymer, or of its corresponding fluorinated sulfonate polymer or fluorinated sulfonic acid polymer.
  • the composition comprises about 90% to about 99.99% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalyst, based on the total weight of the composition.
  • the composition comprises about 92% to about 99.9% by weight of one or more non- crosslinked fluorinated sulfonyl fluoride polymers and about 0.1 % to about 8% by weight of one or more precious metal catalyst; in another aspect, about 95% to about 99.7% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride polymers and about 0.3% to about 5% by weight of one or more precious metal catalyst; about 97% to about 99.5% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride polymers and about 0.5% to about 3% by weight of one or more precious metal catalyst; about 98% to about 99.3% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride polymers and about 0.7% to about 2% by weight of one or more precious metal catalyst; about 98.5% to about 99.3% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride
  • Additional compounds may be present in the composition, but preferably, the composition comprises less than about 5% by weight of any additional compounds, based on the total composition weight. In another aspect, the composition comprises less than about 3% by weight of additional compounds; in another aspect, the composition comprises less than about 2% by weight of additional compounds; in another aspect, the composition comprises less than about 1 % by weight of additional compounds; an in another aspect, the composition comprises less than about 0.5% of additional compounds; or any value, range, or sub-range therebetween; all based on total weight of the composition.
  • Suitable additional compounds include, but are not limited to, radical scavenger compounds, coupling agents, or other resin additives.
  • the composition contains less than 5% by weight of solvent or liquid carrier; in another aspect, less than 2% by weight of solvent or liquid carrier; in another aspect, less than 1 % by weight of solvent or liquid carrier; in another aspect, less than 0.1 % by weight of solvent or liquid carrier; and in another aspect, 0% solvent or liquid carrier; or any value, range, or sub-range therebetween; all based on total weight of the composition.
  • no solvent or liquid carrier is present in the composition, such that the total weight of the composition is the equal to the total dry weight of the composition.
  • the composition can be a solid composition and can be made by a method comprising: a. melting at least one non-crosslinked fluorinated sulfonyl fluoride polymer; b. uniformly distributing at least one precious metal catalyst in the at least one molten non-crosslinked fluorinated sulfonyl fluoride polymer in an amount to form a composition comprising about 90% to about 99.99% by weight of one or more non- crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalysts, based on the total weight of the composition; and c. cooling the mixture of step b to form a solid composition.
  • the precious metal catalyst is combined with the noncrosslinked fluorinated sulfonyl fluoride polymer in the melt.
  • Suitable precious metal catalysts, non-crosslinked fluorinated sulfonyl fluoride polymers, composition, and component amounts are the same as those listed above.
  • Suitable temperatures for steps a and b can be envisioned by one of skill in the art but include temperatures above the melting point of the non-crosslinked fluorinated sulfonyl fluoride polymer where the temperature produces a polymer with a viscosity of suitable level to allow for extrusion.
  • the precious metal catalyst is uniformly distributed in the non-crosslinked fluorinated sulfonyl fluoride polymer, and in one aspect, the precious metal catalyst is uniformly dispersed throughout the non-crosslinked fluorinated sulfonyl fluoride polymer in step b.
  • Uniform distribution step b can occur by any mixing method suitable to distribute or disperse the precious metal catalyst in the resin, such as any mixing method that exerts high mixing and/or shear to the components. These methods include but not limited to mixing in a single-screw extruder or mixing in a twin-screw extruder, where screw elements such as a knead block or gear mixer may also be included.
  • the process further comprises a step of mixing solid non-crosslinked fluorinated sulfonyl fluoride with solid precious metal catalyst prior to melting step a, such that the non-crosslinked fluorinated sulfonyl fluoride polymer is melted in step a with the precious metal catalyst already present.
  • other methods of introducing the precious metal catalyst to the composition may also be used, including but not limited to feeding the precious metal catalyst into the molten non-crosslinked fluorinated sulfonyl fluoride polymer in the mixing apparatus.
  • the precious metal catalyst is highly dispersed within that layer of the membrane to prevent it from agglomerating.
  • a low surface energy molten polymer resin is mixed with a high surface energy filler, operating at a high temperature to reduce the polymer viscosity, and with high shear forces.
  • the precious metal catalyst may have an average particle size D50 less than about 5 pm; in another aspect, about 75 nm; in another aspect, an average particle size D50 less than about 50 nm; and in another aspect, an average particle size D50 less than about 25 nm.
  • the mixture of step b is cooled by any suitable method of reducing temperature.
  • the mixture may simply be cool by removing heat, such as after removing from the heating vessel. Active cooling methods may also be applied to speed the solidification process.
  • the process further comprises a step of shaping the mixture of step b prior to cooling.
  • the mixture of step b may be extruded, pelletized, and cooled.
  • the mixture of step b may be extruded, melt cast, or poured into a film and cooled.
  • the act of cooling or quenching the polymer resin mixture after mixing serves to lock the precious metal catalyst compounds in place to prevent agglomeration and sedimentation, which is a specific difficulty obtained from the current state of the art using a GRC mixed into a PFSA dispersion where the metal catalyst particles are known to settle overtime.
  • Another aspect of the current invention relates to a cation exchange membrane precursor comprising at least one cation exchange precursor layer, where the at least one proton exchange precursor layer comprises about 90% to about 99.99% by weight of one or more non-crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalysts, based on the total weight of the composition, where the one or more precious metal catalyst is uniformly distributed throughout the at least one proton exchange precursor layer.
  • Suitable precious metal catalysts, non-crosslinked fluorinated sulfonyl fluoride polymers, composition components, and component amounts are the same as those listed above.
  • the cation exchange membrane precursor may include at least one additional layer; in another aspect, the cation exchange membrane precursor includes at least two additional layers, where two layers are represented by the terms additional layer and third layer; and in another aspect, the cation exchange membrane precursor includes at least three additional layers, where three layers are represented by the terms additional layer, third layer, and fourth layer.
  • the additional layers may contain an ion exchange resin precursor, such as but not limited to, fluorinated sulfonyl fluoride polymer. Such ion exchange resin precursors may be crosslinkable, crosslinked, or non-crosslinked. In one aspect, the ion exchange resin precursors fall within the IXR or EW ranges described above.
  • the additional layers may be present in the same film as the original cation exchange precursor layer, or they may be one or more separate films that are later joined to form the cation exchange membrane.
  • the at least one additional layers may also independently contain additives, including radical scavengers, precious metal catalysts, other additives, or mixtures thereof.
  • the radical scavengers, precious metal catalysts, and other additives are present in the additional layers in the amounts described above.
  • the composition of the additional layers may be the same or different as the first cation exchange precursor layer, and they also may be the same or different than each other.
  • the additional layer does not contain precious metal catalyst.
  • GRC is most active in certain locations of the membrane, either closer to the anode or cathode depending on the cell operation. Therefore, in one aspect of the invention, there are precious metal catalyst loadings in specific locations of the membrane closest to the anode or cathode, while having no precious metal catalyst in other locations.
  • the cation exchange membrane precursor is unreinforced.
  • a reinforcement layer is present to provide additional mechanical strength to the overall membrane precursor structure. Reinforcement layers can be any material suitable for providing this additional mechanical strength while also allowing cations to move freely through the structure.
  • the reinforcement may be a porous film, woven fabric, or porous scrim material, composed of materials including but not limited to polytetrafluoroethylene (PTFE), polyaryl ether ketone (PAEK), liquid crystal polymer, polyphenylene sulfide (PPS), PTFE-perfluoroalkyl vinyl ether copolymer (PFA), glass, quartz, and polyolefins including polyethylene or polypropylene.
  • PTFE reinforcements include porous expanded PTFE (ePTFE) and woven PTFE. Examples of materials having a high tensile modulus that are suitable as reinforcement materials include liquid crystal polymer, polyphenylene sulfide, glass, quartz, or PAEK.
  • polyaryl ether ketones include, but are not limited to, polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), or polyether ketone ether ketone ketone (PEKEKK).
  • PEK polyether ketone
  • PEEK polyether ether ketone
  • PEKK polyether ketone ketone
  • PEEKK polyether ketone ketone
  • PEKEKK polyether ketone ketone ketone
  • the final cation exchange membrane precursor may have an average thickness of about 25-150 pm; in another aspect, an average thickness of about 30-120 pm; in another aspect, an average thickness of about 30-100 pm; in another aspect, an average thickness of about 30-80 pm; and in another aspect, an average thickness of about 30-60 pm.
  • Lower thicknesses may be desirable to target high efficiency, while higher thicknesses may be desirable to target high durability.
  • the layer within the membrane having precious metal catalyst may have a thickness of about 3 pm to about 150 pm; in another aspect, about 7 pm to about 150 pm; and in another aspect, about 17 to about 150 pm.
  • the layer within the membrane having precious metal catalyst may have a thickness of about 3 pm to about 100 pm; in another aspect, about 7 pm to about 50 pm; and in another aspect, about 17 to about 25 pm.
  • the invention also relates to cation exchange membranes comprising at least one cation exchange layer, where the at least one cation exchange layer comprises about 90% to about 99.99% by weight of one or more non-crosslinked fluorinated sulfonic acid polymers or non-crosslinked fluorinated sulfonate polymers and about 0.01% to about 10% by weight of one or more precious metal catalysts, based on the total weight of the composition, where the one or more precious metal catalyst is uniformly distributed throughout the at least one cation exchange layer. In one aspect, the one or more precious metal catalyst is uniformly distributed.
  • the cation exchange membranes are made by hydrolyzing and optionally protonating the cation exchange membrane precursor, where the non- crosslinked fluorinated sulfonyl fluoride polymers as described above are converted to non-crosslinked fluorinated sulfonate polymers or non-crosslinked fluorinated sulfonic acid polymers.
  • Suitable precious metal catalysts, non-crosslinked fluorinated sulfonyl fluoride polymers and their corresponding non-crosslinked fluorinated sulfonates and sulfonic acids, composition, component amounts, and layer structures are the same as those listed above.
  • the cation exchange membranes may also have one or more additional layers, as described above.
  • the one or more additional layers may comprise a cation exchange resin rather than a ion exchange precursor, including but not limited to a fluorinated sulfonate polymer or fluorinated sulfonic acid polymer.
  • ion exchange resins may be crosslinkable, crosslinked, or non-crosslinked.
  • the cation exchange resin fall within the IXR or EW ranges described above.
  • the additional layers may be present in the same film as the original cation exchange layer, or they may be one or more separate films that are later joined to form the cation exchange membrane.
  • the cation exchange membrane may be unreinforced.
  • a reinforcement layer is present to provide additional mechanical strength to the overall membrane precursor structure.
  • Reinforcement layers can be any material suitable for providing this additional mechanical strength while also allowing cations to move freely through the structure. Suitable reinforcement materials are described above.
  • the cation exchange membranes can be made by a method comprising: d. melting at least one non-crosslinked fluorinated sulfonyl fluoride polymer; e. uniformly distributing at least one precious metal catalyst with the at least one molten non-crosslinked fluorinated sulfonyl fluoride polymer in an amount to form a composition comprising about 90% to about 99.99% by weight of one or more non- crosslinked fluorinated sulfonyl fluoride polymers and about 0.01 % to about 10% by weight of one or more precious metal catalysts, based on the total weight of the composition; f.
  • step e forming a layer of material from the composition of step e, where the precious metal catalyst is uniformly distributed throughout the layer; and g. converting the non-crosslinked fluorinated sulfonyl fluoride polymer from the layer of step f to a non-crosslinked fluorinated sulfonic acid polymer or non-crosslinked fluorinated sulfonate polymer.
  • a cathode exchange membrane made by the above method is also envisioned. The cation exchange membrane precursor results from the process above, stopping before the conversion step g.
  • Suitable precious metal catalysts, non-crosslinked fluorinated sulfonyl fluoride polymers and their corresponding non-crosslinked fluorinated sulfonates and sulfonic acids, composition, component amounts, and layer structures are the same as those listed above.
  • suitable temperatures for steps d and e can be envisioned by one of skill in the art but include temperatures above the melting point of the non-crosslinked fluorinated sulfonyl fluoride polymer where the temperature produces a polymer with a viscosity of suitable level to allow for extrusion.
  • the precious metal catalyst is uniformly distributed in the non- crosslinked fluorinated sulfonyl fluoride polymer, and in one aspect, the precious metal catalyst is uniformly dispersed throughout the non-crosslinked fluorinated sulfonyl fluoride polymer in step e.
  • Uniform distribution step e can occur by any mixing method suitable to distribute or disperse the precious metal catalyst in the resin, such as any mixing method that exerts high mixing and/or shear to the components. These methods include but not limited to mixing in a single-screw extruder or mixing in a twin-screw extruder, where screw elements such as a knead block or gear mixer may also be included.
  • the process further comprises a step of mixing solid non-crosslinked fluorinated sulfonyl fluoride with solid precious metal catalyst prior to melting step d, such that the non-crosslinked fluorinated sulfonyl fluoride polymer is melted in step d with the precious metal catalyst already present.
  • other methods of introducing the precious metal catalyst to the composition may also be used, including but not limited to feeding the precious metal catalyst into the molten non-crosslinked fluorinated sulfonyl fluoride polymer in the mixing apparatus.
  • the composition of step e is cooled prior to forming a layer of material in step f.
  • the method further comprises step e1 of shaping and cooling the composition of step e before step f.
  • the mixture of step e is cooled by any suitable method of reducing temperature.
  • the mixture may simply be cool by removing heat, such as after removing from the heating vessel. Active cooling methods may also be applied to speed the solidification process.
  • the process further comprises a step of shaping the mixture of step e prior to cooling.
  • the mixture of step e may be extruded, pelletized, cooled, and remelted prior to step f.
  • the mixture of step e may be extruded or poured directly into a film and cooled.
  • step f the formation of a layer of composition
  • the formation may occur by any suitable means, including extrusion, melt casting, pouring, or pressing a solid composition at elevated temperature.
  • the composition of step e is extruded into a film during step f. Extrusion may be performed using a single-screw extruder or twin-screw extruder, where screw elements such as a knead block or gear mixer may also be included, before extrusion into a film shape.
  • the additional layers may be formed by any suitable means, including extrusion, pouring, or pressing a solid composition at elevated temperature.
  • the additional layers may be combined with the layer of material from step f by any suitable process, including co-extrusion or lamination.
  • the at least one additional layer is formed by coextruding with the layer of step f to form a single film. Such a coextrusion could occur, for example, by providing separate feedstock for the layer of step f and the at least one additional layer, and then joining the feedstocks during extrusion.
  • the at least one additional layer is separately formed and pressed together at elevated temperature with a film having a layer of step f.
  • reinforcement layers may be used in the cation exchange membrane precursors and cation exchange membranes.
  • the process includes applying the composition of step e to a reinforcement material either during the layer formation step f or after layer formation step f.
  • the composition of step e When the composition of step e is applied to the reinforcement during the layer formation step f, it may be extruded and melt laminated onto the reinforcement by any suitable process, including but not limited to extrusion lamination.
  • the composition of step e when the composition of step e is applied to the reinforcement after layer formation step f, it may be laminated by any suitable process, such as but not limited to by double belt lamination, nip roll lamination, vacuum lamination.
  • the extruded film can then be laminated at elevated temperature with the woven reinforcement to fuse the polymer and woven layer together into a composite film according to typical lamination methods, such as by using a lamination roll or a vacuum lamination process.
  • the non-crosslinked fluorinated sulfonyl fluoride of the layer of step f may then be converted in step g to a non-crosslinked fluorinated sulfonate or noncrosslinked fluorinated sulfonic acid.
  • Any convertible polymers from additional layers may be converted simultaneously as part of the same film, a composite film.
  • the film or composite film may be hydrolyzed in an aqueous alkali metal hydroxide solution and acidified by acid, such as nitric acid, to convert the sulfonyl fluoride groups to sulfonic acid or sulfonate groups.
  • Alkali metal hydroxides include but are not limited to NaOH or KOH.
  • a water-soluble organic solvent may be employed in the hydrolysis solution, such as dimethyl sulfoxide (DMSO), N,N- dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, N-ethyl-2- pyrrolidone, methanol, ethanol, isopropanol, butanol, methoxyethoxyethanol, butoxyethanol, butylcarbitol, hexyloxyethanol, octanol, propylene glycol methyl ether, ethylene glycol, ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1- amino-2-propanol, 1-amino-3-propanol, 2-aminoethoxyethanol, 2- aminoethoxyethanol, and 2-amino-2-methyl-1 -propanol.
  • DMSO dimethyl sulfoxide
  • N,N- dimethylformamide N,N-dimethylacetamide
  • the final reinforced ion exchange membranes may have an average thickness of about 30-150 pm; in another aspect, an average thickness of about 30-120 pm; in another aspect, an average thickness of about 30-100 pm; in another aspect, an average thickness of about 30-80 pm; and in another aspect, an average thickness of about 30-60 pm.
  • the cation exchange membranes may be used in catalyst coated membranes, having multiple layers of functional materials. Such catalyst coated membranes may be used in electrolytical systems, for example, a water electrolysis system.
  • the invention relates to a catalyst coated membrane comprising the cation exchange membrane, where the catalyst coated membrane comprises a cathode catalyst layer on one side of the reinforced ion exchange membrane and an anode catalyst layer on another side of the reinforced ion exchange membrane.
  • a catalyst coated membrane may comprise a cathode catalyst layer (CCL) on one side of the ion exchange membrane and an anode catalyst layer (ACL) on another side of the ion exchange membrane.
  • a cathode catalyst layer may be in direct contact with a cation exchange membrane, and the caton exchange membrane may be in further direct contact with anode catalyst layer to make catalyst coated membrane.
  • the cation exchange membrane may comprise multiple layers and may also including a reinforcement layer.
  • the catalyst coated membrane may contain multiple layers of the same material, and it may contain additional layers of functional materials, such as gas diffusion layers, porous transport layers, or bipolar plates.
  • the CCL and ACL may be applied to the ion exchange membrane in the form of a catalyst ink.
  • Catalyst ink compositions often include a catalyst component and a polymer binder, where the polymer binder often includes fluorinated ionomers such as those described above.
  • the polymer used in the CCL and ACL may be the same or different from the polymer used as the fluorinated ionomer of the ion exchange membrane.
  • Catalyst components may include but are not limited to metal particles or carbon-supported metal particles.
  • Specific metals may include but are not limited to platinum, ruthenium, gold, silver, palladium, iridium, rhodium, iron, cobalt, nickel, chromium, tungsten, manganese, vanadium, and alloys thereof.
  • Solvents such as those mentioned for use in the ion exchange dispersion, may be used to aid in application of the catalyst ink to the ion exchange membrane.
  • the CCL and ACL materials may be applied to the ion exchange membrane by any suitable means, including brushing, spraying, notch bar coating, fluid die coating, rod coating, slot-fed knife coating, three-roll coating, or decal transfer.
  • HSAPB High Surface Area Platinum Black having a Pt crystallite size of 5.0-7.5 nm, Pt surface area ECSA of 50 m 2 /g, and total catalyst surface area of 50 m 2 /g; all available from The Fuel Cell Store, College Station, TX.
  • Platinum Black TA HSTDP was a platinum black product having a BET Pt surface area of 27 m2/g, available from Heraeus Precious Metals, Santa Fe Springs, CA.
  • Catalyst ink component I rC>2 was available from Alpha Aesar Premion®, Ward Hill, MA, and catalyst ink component Pt/C was TKK TEC10E50E, available from Tanaka Precious Metals, Tokyo, Japan.
  • TiC>2-supported Pt catalyst was available from Ishifuku Metal Industry Company, Tokyo, Japan.
  • Platinum on carbon catalyst TEC10V50E had a Pt content of 46.8% by weight, a particle size of 23 A as measured by XRD, and a BET Pt surface area of 106.8 m 2 /g, available from TKK, Tokyo, Japan.
  • NationalTM D2020 is an ionomer dispersion available from The Chemours Company, Wilmington, DE.
  • the PEEK reinforcing fabric used was IEM 17-195/70, a plain weave fabric having fibers of approximately 38 pm in diameter, a center-to-center fiber spacing of about 195 pm, open area of about 70%, available from SEFAR, Thai, Switzerland.
  • a catalyst coated membrane was made by spraying a catalyst ink onto the formed membranes, which were affixed to a vacuum plate heated to 80 °C.
  • the anode catalyst ink contained 0.4 mg/cm 2 of I rC>2 and NationalTM D2020 (weight ratio of 0.84:0.16), and the cathode catalyst ink contained 0.1 mg/cm 2 of Pt/C and NationalTM D2020 (weight ratio 0.15:0.85).
  • the H2:Os ratio in the anode exhaust stream of the cell was quantified using Gas Chromatography (GC).
  • GC Gas Chromatography
  • the mixture contained liquid water, oxygen, hydrogen, and water vapor.
  • N2 gas was also added to ensure that the mixture remained below the flammability limit.
  • the mixture was routed through a series of components designed to condense and remove liquid water to protect the GC. Samples were taken continuously until the H2:O2 ratio equilibrated, typically between 5-15 minutes.
  • Samples were sputter coated with osmium to help minimize charging effects in the electron microscope and then analyzed using backscatter mode on a Auriga 60 CrossBeam SEM. Cross-sections of the membrane were prepared using a microtome.
  • the platinum coated sulfonyl fluoride containing fluoropolymer resin pellets were then fed using a loss-in-weight feeder to a 1” diameter twin screw extruder at a polymer feed rate of 2.27 kg/hour and with a screw speed of 150 RPM.
  • the twin screw extruder contained knead block screw elements to help with distributive mixing of the platinum within the fluoropolymer melt.
  • the temperature profile was from 190 °C in the feed throat and increased to 230 °C at the discharge end. Pellets were strand cut to create black pellets containing 1 wt% platinum.
  • a multi-layer film was prepared using a co-extrusion system.
  • a satellite extruder with a 1” single-screw was ted with the platinized sulfonyl fluoride containing fluoropolymer resin pellets from Example 1 .
  • the feed block combined the flows from these two extruders into discreet layers and fed through a die to create a final film with discreet layers of platinized sulfonyl fluoride resin and virgin non-platinized sulfonyl fluoride fluoropolymer resin.
  • the extruders were run at 275 °C and melt cast from a 10 mil die and stretched in the machine direction to a 2 mil final thickness.
  • the films were hydrolyzed in a solution of DMSO I KOH I water as is taught in the art. The films were then acidified in a solution of 20% nitric acid in water before being dried to remove excess water.
  • the pre-hydrolyzed film of Example 2 was melt laminated with a PEEK reinforcing fabric to form a composite film.
  • the laminated films were hydrolyzed in a solution of DMSO I KOH / water as is taught in the art.
  • the PEEK reinforcing fabric used was a plain weave fabric having fibers of approximately 38 pm in diameter, a center-to-center fiber spacing of about 195 pm, open area of about 70%.
  • the films were then acidified in a solution of 20% nitric acid in water before being dried to remove excess water.
  • Example 1 was repeated, except using a screw speed of 300 RPM.
  • the satellite extruder with a 1.5” single-screw was fed with platinized sulfonyl fluoride containing fluoropolymer resin pellets from Example 4.
  • the feed block combined the flows from these two extruders into discreet layers and feeds through a die to create a final film with discreet layers of platinized sulfonyl fluoride resin and virgin non-platinized sulfonyl fluoride fluoropolymer resin.
  • the extruders were run at 270 °C and melt cast from a 33 mil die and stretched in the machine direction to a 2.3 mil final thickness.
  • the films were hydrolyzed in a solution of DMSO I KOH / water as is taught in the art. The films were then acidified in a solution of 20% nitric acid in water before being dried to remove excess water.
  • Example 3 was repeated, using the pre-hydrolyzed film of Example 5, and the resulting membrane was tested for H2:O2 Crossover. Table 1. H 2 :O2 Crossover Performance (%) for Example 6
  • the platinum coated sulfonyl fluoride containing fluoropolymer resin pellets were then fed using a loss-in-weight feeder to a 27 mm diameter twin screw extruder at a polymer feed rate of 9.07 kg/hour and with a screw speed of 200 RPM.
  • the twin screw extruder contained knead block screw elements to help with distributive mixing of the platinum within the fluoropolymer melt.
  • the temperature profile was from 160 °C in the feed throat and increased to 190 °C at the discharge end. Pellets were strand cut to create black pellets containing 2 wt% platinum.
  • Example 5 was repeated, except the fluoropolymer resin pellets of Example 7 were used in place of the resin pellets from Example 4.
  • Example 3 was repeated, using the pre-hydrolyzed film of Example 8. The resulting membrane was tested for H 2 :C>2 Crossover.
  • Example 10
  • Example 7 was repeated, except 45 g of TiCk-supported Pt was used, yielding pellets containing 1 wt% Pt/TiC>2.
  • Example 5 was repeated, except the fluoropolymer resin pellets of Example 10 were used in place of the resin pellets from Example 4.
  • Example 3 was repeated, using the pre-hydrolyzed film of Example 11 .
  • the platinum coated sulfonyl fluoride containing fluoropolymer resin pellets were then fed using a loss-in-weight feeder to a 31 mm diameter twin screw extruder at a polymer feed rate of 9.07 kg/hour and with a screw speed of 200 RPM.
  • the twin screw extruder contained knead block screw elements to help with distributive mixing of the platinum within the fluoropolymer melt.
  • the temperature profile was from 160 °C in the feed throat and increased to 190 °C at the discharge end. Pellets were strand cut to create black pellets containing 1 .45 wt% platinum.
  • Example 5 was repeated, except the fluoropolymer resin pellets of Example 13 were used in place of the resin pellets from Example 4.
  • Example 3 was repeated, using the pre-hydrolyzed film of Example 14. The resulting membrane was tested for H2:O2 crossover.
  • Example 5 was repeated, except the fluoropolymer resin pellets of Example 16 were used in place of the resin pellets from Example 4. The resulting film was tested for H2:O2 crossover.
  • Example 3 was repeated, using the pre-hydrolyzed film of Example 17.
  • Example 20
  • Example 5 was repeated, except the fluoropolymer resin pellets of Example 19 were used in place of the resin pellets from Example 4.
  • Example 3 was repeated, using the pre-hydrolyzed film of Example 19.
  • the platinum coated sulfonyl fluoride containing fluoropolymer resin pellets were then fed using a loss-in-weight feeder to a 27 mm diameter twin screw extruder at a polymer feed rate of 6.08 kg/hour and with a screw speed of 100 RPM.
  • the twin screw extruder contained knead block screw elements to help with distributive mixing of the platinum within the fluoropolymer melt.
  • the temperature profile was from 160 °C in the feed throat and increased to 190 °C at the discharge end. Pellets were strand cut to create black pellets containing 3.6 wt% platinum.
  • a 50 pm total membrane, with a 12 pm platinum layer was prepared.
  • the doctor blade was set at a gap to yield a dry film thickness of 12 urn, and the platinized dispersion was solution cast onto a substrate.
  • the cast film and substrate was dried in a relative humidity oven for 30 minutes at 10% RH.
  • the film had a second layer solution cast via doctor blade with non-platinized dispersion at a dry film thickness of 38 pm.
  • the sample was dried in a relative humidity chamber at 10% RH for 30 minutes, then introduced to an oven set at 175 °C for 3 minutes to cure the membrane, yielding a membrane having a Pt content of 20 pg/cm 2 Pt, based on the weight of the membrane.
  • the platinum-containing solid layer had 1 % by weight platinum.
  • Example 17 was repeated, using only a single layer of non-platinized resin pellets but forming a membrane of the same total thickness. Table 2. H 2 :O2 Crossover Performance (%) at 0 hours
  • FIGs. 1-7 illustrate membranes having two distinct layers, one having GRC precious metal catalyst and one without additives. It can be seen from FIGs. 1-7 that the current process provides distinct GRC layers having precious metal catalyst uniformly distributed and dispersed throughout the material. This allows coextrusion with a different material layer to form membrane materials having precious metal catalyst with uniform distribution in a desired location while also minimizing the amount of precious metal catalyst needed for the entire membrane. Membranes can be configured to minimize hydrogen and oxygen crossover for multiple end-use applications by purposefully placing the precious metal catalyst in a desired location. By contrast, FIG. 7 shows a membrane formed by a casting process having two layers, where the precious metal catalyst is not uniformly distributed throughout the bottom cast GRC layer.
  • the precious metal catalyst is agglomerated and concentrated at one side of the GRC cast layer such that it is in contact with the non- GRC layer.
  • the precious metal catalyst is not able to customize and configure the layering of precious metal catalyst within the membrane to the effect that it could be done using the present inventive process.

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Abstract

La présente invention concerne une composition comprenant d'environ 90% à environ 99,99% en poids d'un ou plusieurs polymères de fluorure de sulfonyle fluoré non réticulés et d'environ 0,01% à environ 10% en poids d'un ou plusieurs catalyseurs métaux précieux, sur la base du poids total de la composition, le ou les catalyseurs métaux précieux étant uniformément répartis dans le ou les polymères de fluorure de sulfonyle fluoré non réticulés. Une telle composition peut être transformée, par exemple par extrusion, en un précurseur d'échange de cations et, après traitement, une membrane échangeuse de cations. Les films et membranes obtenus présentent un catalyseur métal précieux réparti uniformément dans toute la couche de polymère contenant le catalyseur.
PCT/US2024/021511 2023-03-27 2024-03-26 Polymères de fluorure de sulfonyle fluorés composés et membranes échangeuses d'ions fabriquées à partir de ceux-ci Ceased WO2024206331A1 (fr)

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JP2025554908A JP2026513171A (ja) 2023-03-27 2024-03-26 配合フッ素化スルホニルフルオリドポリマー及びそれから作製されるイオン交換膜
KR1020257035133A KR20250169563A (ko) 2023-03-27 2024-03-26 배합된 플루오르화 설포닐 플루오라이드 중합체 및 이로부터 제조된 이온 교환 막
AU2024247425A AU2024247425A1 (en) 2023-03-27 2024-03-26 Compounded fluorinated sulfonyl fluoride polymers and ion exchange membranes made therefrom
EP24719426.9A EP4689235A1 (fr) 2023-03-27 2024-03-26 Polymères de fluorure de sulfonyle fluorés composés et membranes échangeuses d'ions fabriquées à partir de ceux-ci
CN202480018357.4A CN120898031A (zh) 2023-03-27 2024-03-26 复合氟化磺酰氟聚合物和由其制备的离子交换膜

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CN120898031A (zh) 2025-11-04

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