CN117480644A - 质子交换膜状物 - Google Patents
质子交换膜状物 Download PDFInfo
- Publication number
- CN117480644A CN117480644A CN202280038725.2A CN202280038725A CN117480644A CN 117480644 A CN117480644 A CN 117480644A CN 202280038725 A CN202280038725 A CN 202280038725A CN 117480644 A CN117480644 A CN 117480644A
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- CN
- China
- Prior art keywords
- pvdf
- membrane
- alpha
- material according
- vinylidene fluoride
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
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- 239000012528 membrane Substances 0.000 title claims abstract description 86
- 239000000446 fuel Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 95
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 85
- 239000000178 monomer Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 34
- -1 bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, chlorotrifluoropropylene, ethylene Chemical group 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 18
- 150000002825 nitriles Chemical class 0.000 claims description 15
- 239000005518 polymer electrolyte Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 10
- 229920001519 homopolymer Polymers 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229920006260 polyaryletherketone Polymers 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- NGCJVMZXRCLPRQ-UHFFFAOYSA-N 2-methylidenepentanedinitrile Chemical compound N#CC(=C)CCC#N NGCJVMZXRCLPRQ-UHFFFAOYSA-N 0.000 claims description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000035699 permeability Effects 0.000 claims description 6
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- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
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- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
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- IHXNSHZBFXGOJM-HWKANZROSA-N (e)-2-methylbut-2-enenitrile Chemical compound C\C=C(/C)C#N IHXNSHZBFXGOJM-HWKANZROSA-N 0.000 claims description 3
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- SRXJYTZCORKVNA-UHFFFAOYSA-N 1-bromoethenylbenzene Chemical compound BrC(=C)C1=CC=CC=C1 SRXJYTZCORKVNA-UHFFFAOYSA-N 0.000 claims description 3
- DAEXAGHVEUWODX-UHFFFAOYSA-N 1-fluoroethenylbenzene Chemical compound FC(=C)C1=CC=CC=C1 DAEXAGHVEUWODX-UHFFFAOYSA-N 0.000 claims description 3
- SIZDIMDMQQFWLM-UHFFFAOYSA-N 1-methoxyethenylbenzene Chemical compound COC(=C)C1=CC=CC=C1 SIZDIMDMQQFWLM-UHFFFAOYSA-N 0.000 claims description 3
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 claims description 3
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
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- 238000006277 sulfonation reaction Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 230000005865 ionizing radiation Effects 0.000 claims description 2
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- 229920001169 thermoplastic Polymers 0.000 claims description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000002245 particle Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 239000003792 electrolyte Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
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- FPBWSPZHCJXUBL-UHFFFAOYSA-N 1-chloro-1-fluoroethene Chemical group FC(Cl)=C FPBWSPZHCJXUBL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- LDTMPQQAWUMPKS-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=CCl LDTMPQQAWUMPKS-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
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- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
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- 238000005266 casting Methods 0.000 description 2
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- 125000003700 epoxy group Chemical group 0.000 description 2
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- 238000010101 extrusion blow moulding Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002918 oxazolines Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- 150000003460 sulfonic acids Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 2
- MTKHTBWXSHYCGS-OWOJBTEDSA-N (e)-1-chloro-2-fluoroethene Chemical group F\C=C\Cl MTKHTBWXSHYCGS-OWOJBTEDSA-N 0.000 description 1
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 1
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229920006120 non-fluorinated polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Chemical group 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
-
- H—ELECTRICITY
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Abstract
本发明涉及质子交换膜状物、制备所述膜状物的方法以及所述膜状物在需要离子交换的领域(诸如污水净化和电化学或能量领域)中的用途。特别地,这种膜状物被用于燃料电池膜状物的设计中。
Description
技术领域
本发明涉及质子交换膜状物、制备所述膜状物的方法以及所述膜状物在需要离子交换的领域(诸如电化学或能量领域)中的应用。特别地,该膜状物用于燃料电池膜状物的设计中,诸如用于H2/空气或H2/O2燃料电池(这些电池称作“质子交换膜状物燃料电池”,缩写PEMFC)或甲醇/空气燃料电池(这些电池称作“直接甲醇燃料电池”,缩写DMFC)的质子传导膜状物。
背景技术
燃料电池是电化学发生器,其在氧化剂的存在下将燃料氧化反应的化学能转化成电能、热和水。通常,燃料电池包括多个串联安装的电化学电池,每个电池包括通过充当固体电解质的质子交换膜状物分开的极性相反的两个电极。所述膜状物允许在燃料在阳极处氧化期间形成的质子向阴极传递。
所述膜状物构成燃料电池的核,并且它们因此必须具有良好的质子传导性能以及对反应性气体(对于PEMFC燃料电池,为H2/空气或H2/O2;对于DMFC燃料电池,为甲醇/空气)的低透过性。构成所述膜状物的材料的性质基本上是热稳定性、耐水解性和耐氧化性,以及一定程度的机械柔韧性。
通常使用并满足这些要求的膜状物是由例如属于聚砜、聚醚酮、聚苯和聚苯并咪唑家族的聚合物获得的膜状物。然而,已经发现这些非氟化聚合物在燃料电池环境中相对快速地降解,并且它们的使用寿命暂时不足以用于PEMFC应用。
大多数质子交换膜状物都是基于全氟化聚合物化学,所述全氟化聚合物具有带有磺酸官能团的长或短分支。除了它们的高成本之外,这些各种聚合物具有低的对羟基的耐受性(这限制了它们在燃料电池环境中的耐久性),和低的机械强度。此外,这些膜状物具有离子传导性/氢透过性比率,该比率使得不能够获得结合了高不透过性和高传导性的薄膜状物。此外,全氟化膜状物具有不允许它们在80℃以上的温度下长时间运行的温度使用限制。
为了在80℃以上的温度下获得在质子传导方面的长期效益,一些作者提出了更复杂的材料,该材料除了聚合物基质外,还包含质子传导粒子,因此导电性不再仅仅归因于构成膜状物的聚合物。申请WO 2014/173885就是这种情况,它描述了包含聚合物基质和由无机离子交换粒子组成的填料的复合材料,所述粒子在氟化聚合物基质内原位合成。这些膜状物表现出无机粒子在聚合物基质内的更均匀分布。然而,这种类型的膜状物具有与单独由聚合物基质制成的膜状物相比的较低机械性质、由于燃料电池运行期间尺寸的变化而在粒子-基质界面处有气穴的风险,并且难以在工业规模上制造。
通过辐射诱导的接枝所生产的离子传导膜状物是提高它们的化学稳定性的另一种选择。辐射诱导的接枝反应通过单体在膜中的扩散和单体聚合反应来控制。反应从经辐照的膜的表面处开始,并逐渐移动通过膜的主体。已经描述了基于乙烯-四氟乙烯(ETFE)、氟化乙烯-丙烯(FEP)和乙烯-氯三氟乙烯(ECTFE)的膜,特别是对于两性离子交换膜状物。
确实需要具有改善的性质、特别是改善的耐热性和更高的传导性/气体透过性比率的质子交换膜状物。
发明内容
为了克服上述缺点,本发明人开发了膜状物,该膜状物具有从粉末形式的基于偏二氟乙烯基聚合物(PVDF)开始获得的非常特殊的形态。
根据第一方面,本发明涉及由粉末形式的经辐照的PVDF组成的材料,在该粉末形式的经辐照的PVDF上接枝有苯乙烯类单体和腈类单体,所述经辐照和接枝的PVDF带有质子交换磺酸根基团。
所述PVDF选自聚(偏二氟乙烯)均聚物和偏二氟乙烯与至少一种共聚单体的共聚物,所述共聚单体选自:氟乙烯、四氟乙烯、六氟丙烯、3,3,3-三氟丙烯、2,3,3,3-四氟丙烯、1,3,3,3-四氟丙烯、六氟异丁烯、全氟丁基乙烯、1,1,3,3,3-五氟丙烯、1,2,3,3,3-五氟丙烯、全氟(丙基乙烯基醚)、全氟(甲基乙烯基醚)、溴三氟乙烯、氯氟乙烯、氯三氟乙烯、氯三氟丙烯、乙烯以及它们的混合物。
根据第二方面,本发明涉及制备所述材料的方法,所述方法包括用苯乙烯类和腈类单体的混合物接枝经辐照的PVDF粉末,随后通过磺化对如此辐照和接枝的PVDF粉末进行后处理。
根据第三方面,本发明涉及质子交换聚合物电解质膜状物,所述膜状物由从所述PVDF材料获得的膜组成。
根据第四方面,本发明涉及由粉末形式的所述经辐照、接枝和官能化的PVDF材料制造质子交换聚合物电解质膜状物的方法,所述方法包括将PVDF粉末转化为膜形式。
根据另一个方面,本发明涉及质子交换聚合物复合膜状物,所述膜状物由通过溶剂和/或水途径用所述PVDF材料浸渍的多孔聚合物载体组成。
根据另一个方面,本发明涉及质子交换聚合物复合膜状物,所述膜状物至少部分由所述PVDF材料的纤维组成,其余为聚合物,并通过静电纺丝制造。然后通过溶剂或水途径用所述PVDF材料浸渍该膜状物。
根据另一方面,本发明涉及质子交换聚合物电解质膜状物在以下领域中的应用:
-燃料电池,例如H2/空气或H2/O2燃料电池或甲醇/空气燃料电池;
-电解槽;
-锂电池,所述膜状物有可能是电解质的组成的一部分。
本发明使得克服现有技术的缺点成为可能。更具体地,它提供一种使得以下成为可能的技术:
-针对低于140℃的温度,提高膜在无流动的情况下的耐热性(热阻);
-提高与商业NAFION型膜状物相比的对羟基自由基的耐受性;
-提高与现有技术相比的传导性/氢透过性比率。
具体实施方式
现在将在以下描述中以非限制性方式更详细地描述本发明。
根据第一方面,本发明涉及由粉末形式的经辐照的PVDF组成的材料,在该粉末形式的经辐照的PVDF上接枝有苯乙烯类单体和腈类单体,所述经辐照和接枝的PVDF带有质子交换磺酸根基团。
根据另一方面,本发明涉及质子交换聚合物电解质膜状物,所述膜状物由所述PVDF材料获得。
根据各种实施方案,所述材料和所述膜状物包括在适当的情况下组合的以下特征。除非另外指出,否则所示含量均以重量表示。
PVDF
本发明中使用并通过缩写PVDF表示的含氟聚合物是基于偏二氟乙烯的聚合物。
根据一个实施方案,PVDF是聚(偏二氟乙烯)均聚物或偏二氟乙烯均聚物的混合物。
根据一个实施方案,PVDF是聚(偏二氟乙烯)均聚物或偏二氟乙烯与至少一种与偏二氟乙烯相容的共聚单体的共聚物。
与偏二氟乙烯相容的共聚单体可以被卤化(氟化、氯化或溴化)或未被卤化。
合适的氟化共聚单体的实例是:氟乙烯、四氟乙烯、六氟丙烯、三氟丙烯并且特别是3,3,3-三氟丙烯、四氟丙烯并且特别是2,3,3,3-四氟丙烯或1,3,3,3-四氟丙烯、六氟异丁烯、全氟丁基乙烯、五氟丙烯并且特别是1,1,3,3,3-五氟丙烯或1,2,3,3,3-五氟丙烯、全氟烷基乙烯醚并且特别是具有通式Rf-O-CF=CF2的那些,Rf是烷基、优选C1至C4烷基(优选实例是全氟丙基乙烯基醚和全氟甲基乙烯基醚)。
氟化单体可以包含氯或溴原子。它特别地可以选自溴三氟乙烯、氯氟乙烯、氯三氟乙烯和氯三氟丙烯。氯氟乙烯可以表示1-氯-1-氟乙烯或1-氯-2-氟乙烯。1-氯-1-氟乙烯异构体是优选的。氯三氟丙烯优选地是1-氯-3,3,3-三氟丙烯或2-氯-3,3,3-三氟丙烯。
VDF共聚物还可以包含非卤化单体,诸如乙烯,和/或丙烯酸类或甲基丙烯酸类共聚单体。
含氟聚合物优选含有至少50摩尔%的偏二氟乙烯。
根据一个实施方案,PVDF是偏二氟乙烯(VDF)和六氟丙烯(HFP)的共聚物(P(VDF-HFP)),其具有相对于共聚物的重量为1重量%至35重量%、优选2重量%至23重量%、优选4重量%至20重量%的重量百分比的六氟丙烯单体单元。
根据一个实施方案,PVDF是聚(偏二氟乙烯)均聚物和VDF-HFP共聚物的混合物。
根据一个实施方案,本发明的偏二氟乙烯共聚物是可熔融转化的非均相热塑性共聚物,并且包含两个或更多个共连续相,所述共连续相包含:
a)25重量%至50重量%的第一共连续相,其包含90重量%至100重量%的偏二氟乙烯单体单元和0重量%至10重量%的至少一种另外的含氟单体单元,和
b)大于50重量%至75重量%的第二共连续相,其包含65重量%至95重量%的偏二氟乙烯单体单元和一种或多种选自六氟丙烯和全氟(乙烯基醚)的共聚单体,以引起第二共连续相与第一共连续相的相分离。
所述非均相共聚物含有在固体状态下产生共连续结构的两个或更多个相。共连续相彼此不同,并且可以用扫描电子显微镜(SEM)观察。根据本发明的非均相共聚物不同于包含单相的均相共聚物。
根据一个实施方案,PVDF是两种或更多种VDF-HFP共聚物的混合物。
根据一个实施方案,PVDF包含带有以下官能团中的至少一种的单体单元:羧酸、羧酸酐、羧酸酯、环氧基(例如缩水甘油基)、酰胺、羟基、羰基、巯基、硫化物、噁唑啉、酚、酯、醚、硅氧烷、磺酸、硫酸、磷酸或膦酸。根据本领域技术人员熟知的技术,通过化学反应引入该官能团,所述化学反应可以是氟化单体与带有至少一个所述官能团和能够与氟化单体共聚的乙烯基官能团的单体的接枝或共聚。
根据一个实施方案,所述官能团带有羧酸官能团,所述羧酸官能团是选自丙烯酸、甲基丙烯酸、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯和(甲)丙烯酸羟乙基己酯的(甲基)丙烯酸类型基团。
根据一个实施方案,带有羧酸官能团的单元另外含有选自氧、硫、氮和磷的杂原子。
根据一个实施方案,所述官能团经由在合成过程期间使用的转移剂引入。转移剂是摩尔质量小于或等于20 000g/mol并且带有选自以下基团的官能团的聚合物:羧酸、羧酸酐、羧酸酯、环氧基(诸如缩水甘油基)、酰胺、羟基、羰基、巯基、硫化物、噁唑啉、酚、酯、醚、硅氧烷、磺酸、硫酸、磷酸或膦酸。这种类型的转移剂的一个实例是丙烯酸的低聚物。
PVDF中官能团的含量为至少0.01摩尔%、优选至少0.1摩尔%、且至多15摩尔%、优选至多10摩尔%。
PVDF优选具有高分子量。此处使用的术语“高分子量”应理解为意指熔体粘度大于100Pa.s、优选大于500Pa.s、更优选大于1000Pa.s、有利地大于2000Pa.s的PVDF。根据标准ASTM D3825,使用毛细管流变仪或平行板流变仪在232℃、100s-1的剪切梯度下测量粘度。这两种方法给出了相似的结果。
本发明中使用的PVDF均聚物和VDF共聚物可以通过已知的聚合方法获得,诸如乳液聚合。
根据一个实施方案,它们是在没有氟化表面活性剂的情况下通过乳液聚合方法制备的。
PVDF的聚合产生通常具有按重量计10%至60%、优选10%至50%的固体含量,并且具有小于1微米、优选小于1000nm、优选小于800nm且更优选小于600nm的重均粒度的乳胶。粒子的重均尺寸通常为至少10nm、优选至少50nm,并且有利地平均尺寸在100至400nm的范围内。聚合物粒子可以形成称为二次粒子的团聚体,其重均尺寸小于5000μm、优选小于1000μm,有利地在1和80微米之间、优选为2至50微米。团聚体在配制和施用于基材期间可分解成离散的粒子。
根据一些实施方案,PVDF均聚物和VDF共聚物由生物基VDF组成。术语“生物基”意思是“源自生物质”。这使得改善膜状物的生态足迹成为可能。生物基VDF的特征可以在于,至少1at%的可再生碳(即源自生物材料或生物质的天然来源的碳)的含量,如根据标准NFEN 16640,通过14C的含量测定的。术语“可再生碳”表明碳是天然来源的,并且源自生物材料(或源自生物质),如下所示。根据一些实施方案,VDF的生物碳含量可以大于5%、优选大于10%、优选大于25%、优选大于或等于33%、优选大于50%、优选大于或等于66%、优选大于75%、优选大于90%、优选大于95%、优选大于98%、优选大于99%、有利地等于100%。
乳液聚合能够生产约200nm粒子的乳胶,其在干燥后,例如喷雾干燥后,导致获得体积平均直径(Dv50)在10至50μm范围内的粒子。
粉末形式的PVDF材料
根据本发明的材料由粉末形式的经辐照的PVDF组成,在该粉末形式的经辐照的PVDF上接枝有苯乙烯类单体和腈类单体,所述经辐照和接枝的PVDF带有质子交换磺酸根基团。
该材料是根据以下方法制备的,该方法包括用苯乙烯类和腈类单体的混合物接枝经辐照的PVDF,随后通过磺化对如此辐照和接枝的PVDF粉末进行后处理。
下面详细介绍了该方法的每个步骤。
在一个实施方案中,首先将PVDF粉末暴露于电离辐射以将活性位点引入PVDF聚合物链中。通过电子束、伽马射线或X射线源以在25和150千戈瑞(kgray)之间、优选在30和125kg千戈瑞之间的剂量辐照粉末。辐照是在真空下、空气下或氮气下进行的。由此获得经辐照的PVDF粉末。然后使用包含苯乙烯类单体和腈类单体的单体混合物对经辐照的PVDF粉末进行接枝步骤。
根据一个实施方案,所述苯乙烯类单体为α-烷基苯乙烯型,其中烷基选自:甲基、乙基、丙基、丁基、戊基和己基。
根据一个实施方案,所述苯乙烯类单体选自:α-甲基苯乙烯、α-氟苯乙烯、α-溴苯乙烯、α-甲氧基苯乙烯和α,β,β-三氟苯乙烯。
根据一个实施方案,所述苯乙烯类单体是α-甲基苯乙烯(AMS)。
根据一个实施方案,所述腈类单体选自丙烯腈、2-甲基-2-丁烯腈、2-亚甲基戊二腈和甲基丙烯腈。
根据一个实施方案,在用异丙醇冲洗之前,将经接枝的PVDF粉末通入60℃的含有在30%和50%之间的α-甲基苯乙烯、在30%和50%之间的亚甲基戊二腈和在0和40%之间的异丙醇的浴中。
根据一个实施方案,苯乙烯类单体/腈类单体摩尔比范围为0.7至1.3。
根据一个实施方案,所述腈类单体是2-亚甲基戊二腈(MGN)。
根据一个实施方案,PVDF粉末在包含所述苯乙烯类单体和所述腈类单体的单体混合物的存在下被辐照。通过电子束、伽马射线或X射线源以在25和150千戈瑞(kgray)之间、优选在30和125kg千戈瑞之间的剂量辐照粉末。辐照是在真空下、空气下或氮气下进行的。
然后将经辐照和接枝的PVDF粉末与氯磺酸进行后官能化反应,随后在水中或碱性溶液中水解。这使得阳离子交换-SO3H官能团能够被引入到PVDF上。
根据一个实施方案,经接枝的粉末的磺化在室温下在含有氯磺酸的二氯甲烷溶液中进行。
然后用蒸馏水冲洗带有共价键合的-SO3H官能团的经接枝的PVDF粉末,直到冲洗水具有中性pH,然后在80℃下水解,然后在空气中干燥。由此转化的粉末的重量增加25%至60%、优选增加35%至55%。
经由基于相对于PVDF参考峰的芳族基团的特定峰和/或腈基的特定峰的面积之间的比率的校准曲线,通过透射红外(IR)光谱的测量显示出按重量计在25%和60%之间、优选在35%和55%之间的粉状PVDF的接枝度。
聚合物电解质膜状物
根据另一个方面,本发明涉及由粉末形式的所述经辐照、接枝和官能化的PVDF材料生产质子交换聚合物电解质膜状物的方法,所述方法包括将PVDF粉末转化为构成膜状物的膜的形式。将PVDF粉末转化为膜形式的这一步骤通过本领域技术人员已知的任何技术进行:挤出吹塑、平膜挤出,但也有例如通过溶剂浇铸(流延)的膜生产。
根据另一方面,本发明涉及质子交换聚合物电解质膜状物,所述膜状物由从所述PVDF材料获得的膜组成。
根据另一个方面,本发明涉及由粉末形式的所述经辐照、接枝和官能化的PVDF材料与选自聚甲基丙烯酸甲酯及其共聚物、含氟聚合物、聚氨酯和聚酯的另外的聚合物的混合物生产质子交换聚合物电解质膜状物的方法。所述混合物包含按重量计100%至50%的粉末形式的所述经辐照、接枝和官能化的PVDF。该方法包括将混合物转化为膜形式。将混合物转化为膜形式的该步骤通过本领域技术人员已知的任何技术进行:挤出吹塑、平膜挤出,但也有例如通过溶剂浇铸(流延)的膜生产。
根据另一个方面,本发明涉及质子交换聚合物复合膜状物,所述膜状物由通过溶剂和/或水途径用所述PVDF材料浸渍的多孔载体组成,所述多孔载体是选自以下的聚合物:聚乙烯、聚丙烯、聚四氟乙烯(PTFE)、聚(偏二氟乙烯)(PVDF)、聚砜(PSU)、聚醚砜(PESU)、聚酰亚胺(PI)、聚芳醚酮(PAEK)家族诸如PEEK或PEKK。这种多孔载体可以根据本领域技术人员已知的技术生产,诸如相转化、挤出随后顺序拉伸、熔喷或纺粘挤出、或静电纺丝。
根据另一个方面,本发明涉及质子交换聚合物复合膜状物,所述膜状物至少部分由所述PVDF材料的纤维组成,其余为选自以下的聚合物之一:聚甲基丙烯酸甲酯及其共聚物、含氟聚合物、聚氨酯、聚酯、聚乙烯、聚丙烯、聚四氟乙烯(PTFE)、聚(偏二氟乙烯)(PVDF)、聚砜(PSU)、聚醚砜(PESU)、聚酰亚胺(PI),以及聚芳醚酮(PAEK)家族诸如PEEK或PEKK。这种复合膜状物是通过静电纺丝生产的。该膜状物随后通过溶剂或水途径用所述PVDF材料浸渍。
有利地,电解质膜状物的离子交换容量(IEC)大于0.6mmol/g。IEC的测量如下:在搅拌下将1cm×1cm样品浸入0.5M的KCl溶液中过夜。溶液中存在的氢离子在与磺酸根基团上的K+交换后,之后用0.05M KOH溶液滴定至pH=7。然后根据以下方程式计算离子交换容量:
其中n(H+)是质子的摩尔数,W干是以其H+形式的干膜状物的重量,c(KOH)是KOH的浓度,V(KOH)是加入用于滴定的KOH溶液的体积,WK是以其K+形式的干膜状物的重量,并且M(K+)和M(H+)是质量。
有利地,根据一个实施方案,根据本发明的电解质膜状物的氢透过性小于2mA/cm2。为了该测量,将膜状物放置在燃料电池的腔室中,然后在阴极处施加氢气流,同时在阳极处施加氮气流。然后在两侧施加电势,并测量通过氢气传输通过膜状物而获得的电流。
有利地,根据一个实施方案,根据本发明的电解质膜状物的氢透过性小于2×10- 2mL/min.cm2。为了该测量,将膜状物放置在与气相色谱仪相连的渗透计的腔室中。用氦气吹扫渗透计腔室,然后在0.1MPa的压力下将氢气流施加到膜状物的上表面。然后通过气相色谱法测量扩散通过膜状物进入下部的氢气流。
-40℃和140℃之间的动态力学分析(DMA)表明膜状物不会熔化。对于20μm的膜厚度,在23℃、50%相对湿度下以20mm/分钟的速度测量的其断裂伸长率大于100%。
在膜状物电极组件(MEA)中,这种粉末可以用作催化剂、另外的电子传导添加剂和膜状物之间的粘合剂。
根据另一方面,本发明涉及质子交换聚合物电解质膜状物在以下领域中的应用:
-燃料电池,例如H2/空气或H2/O2燃料电池或甲醇/空气燃料电池;
-电解槽;
-锂电池,所述膜状物有可能是电解质的组成的一部分。
根据一个实施方案,聚合物电解质膜状物旨在插入电极-膜状物-电极组件内的燃料电池装置中。
这些膜状物有利地为具有例如10至200微米的厚度的薄膜形式。
为了制备这样的组件,可以将膜状物放置在两个电极之间。然后在适当的温度下压制由布置在两个电极之间的膜状物形成的组件,以获得良好的电极-膜状物粘附性。
然后将电极-膜状物-电极组件放置在两个板之间,确保导电和向电极供应反应物。这些板通常被称为双极板。
Claims (19)
1.由粉末形式的经辐照的PVDF组成的材料,在所述粉末形式的经辐照的PVDF上接枝有苯乙烯类单体和腈类单体,所述经辐照和接枝的PVDF带有质子交换磺酸根基团。
2.根据权利要求1所述的材料,其中苯乙烯类单体/腈类单体摩尔比范围为0.7至1.3。
3.根据权利要求1和2中任一项所述的材料,其中所述PVDF选自聚(偏二氟乙烯)均聚物和偏二氟乙烯与至少一种共聚单体的共聚物,所述共聚单体选自:氟乙烯、四氟乙烯、六氟丙烯、3,3,3-三氟丙烯、2,3,3,3-四氟丙烯、1,3,3,3-四氟丙烯、六氟异丁烯、全氟丁基乙烯、1,1,3,3,3-五氟丙烯、1,2,3,3,3-五氟丙烯、全氟(丙基乙烯基醚)、全氟(甲基乙烯基醚)、溴三氟乙烯、氯氟乙烯、氯三氟乙烯、氯三氟丙烯、乙烯以及它们的混合物。
4.根据权利要求1至3中的一项所述的材料,其中所述PVDF是偏二氟乙烯均聚物。
5.根据权利要求1至3中的一项所述的材料,其中所述PVDF是偏二氟乙烯和六氟丙烯的共聚物,其具有相对于共聚物的重量为1重量%至35重量%、优选2重量%至23重量%、优选4重量%至20重量%的重量百分比的六氟丙烯单体单元。
6.根据权利要求1至3中的一项所述的材料,其中所述PVDF是非均相热塑性共聚物,并且包含两个或更多个共连续相,所述共连续相包含:
a)25重量%至50重量%的第一共连续相,其包含90重量%至100重量%的偏二氟乙烯单体单元和0重量%至10重量%的至少一种另外的含氟单体单元,和
b)大于50重量%至75重量%的第二共连续相,其包含65重量%至95重量%的偏二氟乙烯单体单元和一种或多种选自六氟丙烯和全氟(乙烯基醚)的共聚单体,以引起所述第二共连续相与所述第一共连续相的相分离。
7.根据权利要求1至6中的一项所述的材料,其中所述苯乙烯类单体选自:α-甲基苯乙烯、α-氟苯乙烯、α-溴苯乙烯、α-甲氧基苯乙烯和α,β,β-三氟苯乙烯。
8.根据权利要求1至7中的一项所述的材料,其中所述腈类单体选自丙烯腈、2-甲基-2-丁烯腈、2-亚甲基戊二腈和甲基丙烯腈。
9.根据权利要求1至8中的一项所述的材料,其中所述PVDF用α-甲基苯乙烯和2-亚甲基戊二腈接枝,并用氯磺酸官能化。
10.制备根据权利要求1至9中的一项所述的材料的方法,所述方法包括用苯乙烯类和腈类单体的混合物接枝经辐照的PVDF粉末,随后通过磺化对如此辐照和接枝的PVDF粉末进行后处理。
11.根据权利要求10所述的方法,包括以下步骤:
-将所述PVDF粉末暴露于选自电子束、伽马射线或X射线的电离辐射;
-将所述经辐照的粉末暴露于单体的混合物,所述单体的混合物包含选自α-甲基苯乙烯、α-氟苯乙烯、α-溴苯乙烯、α-甲氧基苯乙烯和α,β,β-三氟苯乙烯的苯乙烯类单体,以及选自丙烯腈、2-甲基-2-丁烯腈、2-亚甲基戊二腈和甲基丙烯腈的腈类单体;
-使经接枝的PVDF粉末与氯磺酸进行后官能化反应,随后在水中或碱性溶液中水解。
12.由权利要求1至9中任一项所述的PVDF材料生产质子交换聚合物电解质膜状物的方法,所述方法包括将PVDF粉末转化为膜形式。
13.由权利要求1至9中任一项所述的PVDF材料和选自以下的另外的聚合物的混合物生产质子交换聚合物电解质膜状物的方法:聚甲基丙烯酸甲酯及其共聚物、含氟聚合物、聚氨酯和聚酯,所述方法包括将所述混合物转化成膜形式。
14.质子交换聚合物电解质膜状物,所述膜状物由从权利要求1至9中任一项所述的PVDF材料获得的膜组成。
15.质子交换聚合物复合膜状物,所述膜状物由通过溶剂和/或水途径用权利要求1至9中任一项所述的PVDF材料浸渍的多孔载体组成,所述多孔载体是选自以下的聚合物:聚乙烯、聚丙烯、聚四氟乙烯(PTFE)、聚(偏二氟乙烯)(PVDF)、聚砜(PSU)、聚醚砜(PESU)、聚酰亚胺(PI)和聚芳醚酮(PAEK)。
16.质子交换聚合物复合膜状物,所述膜状物至少部分由权利要求1至9中任一项所述的PVDF材料的纤维组成,其余为选自以下的聚合物之一:聚甲基丙烯酸甲酯及其共聚物、含氟聚合物、聚氨酯、聚酯、聚乙烯、聚丙烯、聚四氟乙烯(PTFE)、聚(偏二氟乙烯)(PVDF)、聚砜(PSU)、聚醚砜(PESU)、聚酰亚胺(PI),和聚芳醚酮(PAEK),通过静电纺丝然后通过溶剂或水途径用所述PVDF材料浸渍获得所述膜状物。
17.根据权利要求14至16中的一项所述的膜状物,其具有小于2×10-2mL/min.cm2的氢透过性。
18.根据权利要求14至17中的一项所述的膜状物,其具有通过用0.05MKOH溶液滴定测量的大于0.6mmol/g的离子交换容量(IEC)。
19.燃料电池,其包括根据权利要求14至18中任一项所定义的膜状物。
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- 2022-05-31 WO PCT/FR2022/051032 patent/WO2022254143A1/fr active Application Filing
- 2022-05-31 KR KR1020237044831A patent/KR20240017365A/ko unknown
- 2022-05-31 EP EP22734338.1A patent/EP4348737A1/fr active Pending
- 2022-05-31 JP JP2023573643A patent/JP2024520572A/ja active Pending
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KR20240017365A (ko) | 2024-02-07 |
EP4348737A1 (fr) | 2024-04-10 |
FR3123507A1 (fr) | 2022-12-02 |
JP2024520572A (ja) | 2024-05-24 |
WO2022254143A1 (fr) | 2022-12-08 |
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