CN115991820B - Polymeric phosphonic acid ionic membrane and preparation method thereof - Google Patents
Polymeric phosphonic acid ionic membrane and preparation method thereof Download PDFInfo
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- CN115991820B CN115991820B CN202211269108.1A CN202211269108A CN115991820B CN 115991820 B CN115991820 B CN 115991820B CN 202211269108 A CN202211269108 A CN 202211269108A CN 115991820 B CN115991820 B CN 115991820B
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- phosphonic acid
- polymeric phosphonic
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- ionic membrane
- auxiliary agent
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000012528 membrane Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- -1 phosphonic acid ion Chemical class 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 238000005342 ion exchange Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000007606 doctor blade method Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims 4
- 230000001131 transforming effect Effects 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract 2
- 239000001257 hydrogen Substances 0.000 abstract 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003014 ion exchange membrane Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- HDMTWPVKWCLZNV-UHFFFAOYSA-N sulfuryl difluoride 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FS(F)(=O)=O.FC(F)=C(F)OC(F)=C(F)F HDMTWPVKWCLZNV-UHFFFAOYSA-N 0.000 description 5
- 239000004693 Polybenzimidazole Substances 0.000 description 4
- 229920002480 polybenzimidazole Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 4
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- CGGRLBARTWLNQK-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-1-(1,1,2,2,3,3,3-heptafluoropropoxy)-3-[1,1,2,2,3,3-hexafluoro-3-(1,1,2,2,3,3,3-heptafluoropropoxy)propyl]peroxypropane Chemical compound FC(C(C(OC(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)OOC(C(C(F)(F)OC(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F CGGRLBARTWLNQK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KHNPRCWUXYAIST-UHFFFAOYSA-N OP(O)(=O)OC(F)=C(F)F Chemical group OP(O)(=O)OC(F)=C(F)F KHNPRCWUXYAIST-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 1
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- QARLOMBMXGVKNV-UHFFFAOYSA-N 1,2,2-trifluoroethenesulfonyl fluoride Chemical compound FC(F)=C(F)S(F)(=O)=O QARLOMBMXGVKNV-UHFFFAOYSA-N 0.000 description 1
- MNKLWIRFRFGHEL-UHFFFAOYSA-N 1,2,2-trifluoroethenylphosphonic acid Chemical compound OP(O)(=O)C(F)=C(F)F MNKLWIRFRFGHEL-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005819 Potassium phosphonate Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- FFEOZYZNEUVLSW-UHFFFAOYSA-N disodium;dioxidophosphane Chemical compound [Na+].[Na+].[O-]P[O-] FFEOZYZNEUVLSW-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
Abstract
The invention belongs to the field of fluorine-containing high polymer materials, and provides a polymeric phosphonic acid ionic membrane and a preparation method thereof. The ionic membrane provided by the invention consists of polymeric phosphonic acid resin, a porous fiber reinforced layer material and an auxiliary agent, wherein the polymeric phosphonic acid resin has the following structure:
Description
Technical Field
The invention belongs to the field of fluorine-containing high polymer materials, relates to a polymeric phosphonic acid ionic membrane and a preparation method thereof, and particularly relates to an ionic membrane prepared from fluorine-containing olefin units, perfluorovinyl ether phosphonic acid units, perfluorovinyl phosphoric acid units and perfluorovinyl ether sulfonic acid units and a preparation method thereof.
Background
An ion exchange membrane fuel cell is a power generation device which directly converts chemical energy into electric energy through an electrochemical mode, and is considered to be the first clean and efficient power generation technology in the 21 st century. Ion exchange membranes (proton exchange membrane, PEM) are key materials for ion exchange membrane fuel cells (proton exchange membrane fuel cell, PEMFC).
Ion exchange membrane fuel cells most often use Nafion (i.e., a perfluorosulfonic acid membrane) as their ion conducting membrane, however, nafion must contain a sufficiently high water content to exhibit effective conductivity and therefore operate at temperatures below 90c (most often 70-80 c). The mechanism of ion conduction is a carrying mechanism, namely, ions dissociated by strong acid form hydronium ions with water molecules, and the ions are conducted by the transfer between the water molecules. However, at high temperatures, nafion membranes can significantly reduce ionic conductivity due to the dissipation of water molecules.
Therefore, in order to overcome the problems of the ion conducting membrane of the perfluorinated sulfonic acid membrane under the high temperature condition, a great deal of research on the high temperature resistant ion conducting membrane at home and abroad is developed. Currently, research on ion exchange membranes operating above 100 ℃ is mainly conducted on phosphoric acid doped aromatic heterocyclic polymer proton membranes. For example, chinese patent CN110224166a discloses a phosphoric acid doped cross-linked polybenzimidazole high temperature proton exchange membrane, which is obtained by dissolving polybenzimidazole and hyperbranched polymer (poly-p-chloromethyl styrene) in an organic solvent according to a certain proportion, adding the hyperbranched polymer solution into polybenzimidazole solution, forming a film, soaking in phosphoric acid solution, and drying. The prepared phosphoric acid doped crosslinked polybenzimidazole high-temperature proton exchange membrane has excellent mechanical strength and high-temperature proton conductivity. However, under the low temperature condition, the working efficiency is low, the quick start cannot be realized, and the stability is poor. Therefore, the current phosphoric acid doped polymer proton exchange membrane still cannot meet the practical use requirements of the fuel cell.
Disclosure of Invention
In order to overcome the problems of the fuel cell ion exchange membrane, the invention constructs a polymeric phosphonic acid ion membrane, adopts fluoroolefin/fluorovinyl ether, perfluorovinyl phosphonate monomer, perfluorovinyl ether phosphonate and perfluorovinyl ether sulfonyl fluoride monomer ternary polymerization to obtain perfluorosulfonic acid resin through hydrolytic acidification, and prepares the ion membrane capable of stably operating at a higher temperature (120-150 ℃) so as to break through the bottleneck of the operation of a high temperature region of the fuel cell. Meanwhile, the device can be started quickly and run stably under the low-temperature condition.
The above object of the present invention is achieved by the following technical scheme:
the polymeric phosphonic acid ionic membrane provided by the invention comprises polymeric phosphonic acid resin and an auxiliary agent.
Preferably, the polymeric phosphonic acid ion membrane further comprises a porous fiber reinforced material.
The proton conductivity of the polymeric phosphonic acid ion membrane at 150 ℃ is higher than 60mS/cm.
The polymerized phosphonic acid resin is obtained by polymerizing fluoroolefin/fluorovinyl ether, perfluorovinyl phosphonate monomer, perfluorovinyl ether phosphonate monomer and perfluorovinyl ether sulfonyl fluoride monomer in a multi-component way to obtain a polymerized phosphonic acid resin precursor, and then hydrolyzing and acidifying the precursor, wherein the structural formula is as follows:
wherein k is an integer of 0 to 3, f is an integer of 1 to 4, preferably k=0 to 1, f=2; g is an integer from 0 to 4, preferably g=2; t is an integer from 0 to 3, v is an integer from 1 to 4, preferably t=0-1, v=2; a. b and c are integers from 1 to 20, a ', b ' and c ' are integers from 1 to 3; wherein R is- (OCF) 2 ) m (CF 2 ) n X, X is Cl or F; m and n are integers from 0 to 3; x/(x+y+z) =0.2-0.7, y/(x+y+z) =0.2-0.79, and z/(x+y+z) =0.01-0.1.
The number average molecular weight of the polymeric phosphonic acid resin is 20 to 85 ten thousand, preferably 25 to 60 ten thousand, more preferably 25 to 40 ten thousand.
The ion exchange capacity of the polymeric phosphonic acid resin is 0.5-2.5 mmol/g, preferably 0.9-1.8 mmol/g; more preferably 1.0 to 1.4mmol/g.
In the polymerized phosphonic acid resin, the mole percentage of fluoroolefin/fluorovinyl ether is 30-85.0%, the mole percentage of perfluorovinyl phosphonate polymerization unit is 5-50.0%, the mole percentage of perfluorovinyl ether phosphonate polymerization unit is 5-50.0%, and the mole percentage of perfluorovinyl sulfonyl fluoride is 5-50.0%.
The thickness of the porous fiber reinforced material is 2-50 μm, preferably 5-20 μm. The number of layers of the porous fiber reinforced material in the ionic membrane is 0-10, more preferably 0-5. The porous fiber reinforced material is a homogeneous membrane when 0 layers are formed, and the porous fiber reinforced material is a composite ionic membrane when 1-10 layers are formed.
The porous fiber reinforced material is one or more selected from polytetrafluoroethylene, polyvinylidene fluoride, polyethylene and polypropylene.
The volume percentage of the porous fiber reinforced material in the perfluorinated proton membrane is 5-70%, preferably 10-60%, more preferably 20-50%.
The porous fiber reinforced layer material has a porosity of 60% to 95%, preferably a porosity of 75% to 95%, more preferably 80% to 95%. The gram weight of the porous fiber reinforced material is 2-6 g/m 2 Preferably 2.5 to 5g/m 2 。
The auxiliary agent comprises A and/or B.
Wherein the auxiliary agent A is a metal complex formed by a metal M and a ligand L, and the molar ratio of the metal M to the ligand L is 1:1-1:10; preferably 1:1 to 1:5.
The structural formula of the ligand L in the auxiliary agent A is as follows:
wherein R is 1 ，R 2 ，R 3 ，R 4 Is H, OH, CH 3 (CH 2 ) n1 O，CH 3 (CH 2 ) n1 ，NH 2 ，CH 2 OH，C 6 H 5 ，CF 3 (CF 2 ) n1 ，CF 3 (CF 2 ) n One or more of O, wherein n1 is an integer from 0 to 10;
the metal M is selected from the group consisting of a metal, a metal oxide, a metal salt, and any combination thereof.
Preferably, the metal M is selected from, but not limited to CeO 2 、CePO 4 、Ce(NO 3 ) 3 ·6H 2 O、Ce(SO 4 ) 2 、Ce(OH) 4 、(NH 4 ) 2 Ce(NO 3 ) 6 、Ce 2 (CO 3 ) 3 ·xH 2 O、Ce(CH 3 COO) 3 ·xH 2 O, one or more of the following.
The structural formula of the auxiliary agent B is as follows:
wherein R is 11 ，R 22 ，R 33 ，R 44 Is H, OH, CH 3 (CH 2 ) n2 O，CH 3 (CH 2 ) n2 ，NH 2 ，CH 2 OH，C 6 H 5 ，CF 3 (CF 2 ) n2 ，CF 3 (CF 2 ) n2 One or more of O, wherein n2 is an integer from 0 to 10;
in the polymerized phosphonic acid film, the content of polymerized phosphonic acid resin is 90-99.9 wt%, the content of auxiliary agent is 0.1-10 wt%, wherein the content of auxiliary agent A is 0.05-5 wt%, and the content of auxiliary agent B is 0.05-5 wt%;
preferably, the content of the polymeric phosphonic acid resin is 95-99.9 wt%, and the content of the auxiliary agent is 0.1-5%; wherein the content of the auxiliary agent A is 0.05 to 3 weight percent, and the content of the auxiliary agent B is 0.05 to 2 weight percent.
The invention also provides a preparation method of the polymeric phosphonic acid ionic membrane, which comprises a melt extrusion process and a solution coating process.
The melt extrusion process is specifically as follows:
s1: and preparing the polymerized phosphonic acid ion exchange resin precursor into a base film by adopting a double-screw extruder, and then placing the reinforcing layer on the surface or inside of the base film by adopting a continuous vacuum compounding process to prepare the reinforced composite base film.
S2: and (3) soaking the reinforced composite base film obtained in the step (S1) in an alkali metal hydroxide solution, carrying out hydrolysis transformation, soaking in an acid solution, and washing with deionized water to obtain the final polymerized phosphonic acid ion film.
Wherein, the alkali metal hydroxide in the step S2 is KOH or NaOH aqueous solution; the acid solution is nitric acid, sulfuric acid, hydrochloric acid or a mixed solution thereof.
The specific steps of the solution coating process are as follows: dissolving a polymeric phosphonic acid resin precursor in a solvent, adding an auxiliary agent to disperse to prepare a film-making solution, then taking glass or a porous fiber reinforced layer material as a substrate to form a film, and heating to volatilize the solvent to prepare the polymeric phosphonic acid ionic film.
Wherein the film forming mode comprises the following steps: solution casting, wire rod coating, doctor blade coating, spraying or dipping; the solid content of the film-making liquid is 5-35 wt%; the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone, butanone, 1-5 carbon chain alcohol aqueous solution, formic acid or acetic acid.
The thickness of the prepared polymeric phosphonic acid ion membrane is 8-150 μm, more preferably 8-50 μm.
Compared with the prior art, the invention has at least the following advantages:
1. the polymeric phosphonic acid ion membrane provided by the invention comprises polymeric phosphonic acid resin, has high proton conductivity under high temperature conditions (120-150 ℃), can completely meet the application requirements of the fuel cell proton membrane under high temperature working conditions, ensures the proton conductivity under low temperature conditions (below 100 ℃), and has the capability of wide temperature region working and running. The proton conductivity of the polymeric phosphonic acid ion membrane can reach more than 60mS/cm at 150 ℃.
2. The polymeric phosphonic acid ionic membrane provided by the invention has high ion exchange capacity and good mechanical property, stability and chemical property.
Detailed Description
The following examples are further illustrative of the invention, which is not limited thereto. The embodiment is not specifically described, and the percentage content is mass percentage.
Example 1:
cleaning the reaction kettle, adding 5.0L deionized water and 200g sodium dodecyl benzene sulfonate, starting a stirring device, vacuumizing, filling high-purity nitrogen for three times, testing that the oxygen content in the reaction kettle is below 1ppm, vacuumizing, and adding 100g perfluorovinyl ether phosphate monomer (CF) into the reaction kettle through a liquid feed valve 2 ＝CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -P＝O-(OCH 3 ) 2 ) 120g of perfluorovinyl phosphoric acid monomer (CF) 2 ＝CF-CF 2 -P＝O-(OCH 3 ) 2 ) 100g of perfluorovinyl ether sulfonyl fluoride monomer (CF) 2 ＝CF-O-CF 2 CF(CF 3 )-O-(CF 2 ) 2 -SO 2 F) Then, tetrafluoroethylene monomer was charged into the reaction vessel to a pressure of 0.9MPa, the temperature was raised to 40℃and 10g of perfluoropropoxypropyl peroxide (CF) was added by a metering pump 3 CF 2 CF 2 OCF(CF 3 )CO-OO-COCF(CF 3 )OCF 2 CF 2 CF 3 ) Initiating polymerization reaction, continuously introducing tetrafluoroethylene monomer, keeping the reaction pressure at 0.9MPa, adding 2.0g of initiator into the system every 20min, stopping adding the initiator after 2.5h of reaction, and stopping adding the tetrafluoroethylene monomer after the reaction is continued for 20 min. Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing milky white slurry in the kettle into a post-treatment system through a discharging valve, performing high-speed shearing, demulsification and condensation, filtering and separation to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the polymerized phosphonic acid precursor polymer.
Adding the obtained polymerized phosphonic acid precursor polymer into a transformation tank of potassium hydroxide solution with the temperature of 70 ℃ and the concentration of 20 percent, heating for 48 hours, and obtaining the sulfonyl fluoride (-SO) 2 F) The side group is converted into potassium sulfonate (-SO) 3 K) Form (-PO (OR) in phosphonate ester 2 ) The side group is converted into potassium phosphite (-PO) 3 K 2 ). Washing the resin after salt conversion with pure water for 8 times, adding into nitric acid solution, and adding nitric acid solution (HNO) with nitric acid concentration of 15% by mass 3 ) After 4 times of replacement of the acid liquor by a residence time of 4 hours in the acid liquor at 60 ℃, the acid liquor is rinsed for 4 hours with deionized water at 50 ℃ in a high-purity water tank, and sodium sulfonate (-SO) in the polymer is removed 3 K) The side groups being converted to sulphonate ions (-SO) 3 H) Form (-PO) in sodium phosphonite 3 K 2 ) The side group is converted into phosphorous acid (-PO) 3 H 2 ) To obtain the polymeric phosphonic acid resin.
The ion exchange capacity of the polymerized phosphonic acid resin is 1.5mmol/g, the number average molecular weight is 42 ten thousand, the polymer structure contains 48.5 percent of tetrafluoroethylene polymerization units, 10.5 percent of perfluorovinyl ether phosphonate polymerization units, 20.5 percent of perfluorovinyl phosphonate polymerization units and 20.5 percent of perfluorosulfonyl fluoride vinyl ether polymerization units.
The above polymeric phosphonic acid resin was dissolved in N, N-dimethylformamide to form a dispersion, and 1wt% of the auxiliary a and 0.5wt% of the auxiliary B were added to the dispersion, respectively. Stirring and dispersing uniformly to obtain film-forming liquid with the solid content of 22%, coating the film-forming liquid by a wire rod, and volatilizing the solvent after heating to obtain the polymeric phosphonic acid ionic film with the solid content of 12 mu m.
Wherein R in the ligand (L) in the auxiliary agent A 1 ，R 4 Is C 6 H 5 ，R 2 Is OH, R 3 Is H;
the metal (M) being Ce 2 (CO 3 ) 3 ·xH 2 O；
The ligand (L) and Ce 3+ The molar ratio of (2) is 4:1;
r in the auxiliary B 11 ，R 22 Is OCH 3 ；R 33 ，R 44 H.
The obtained ionic membrane is subjected to infrared spectrogram analysis of 1050cm -1 Where a distinct sulfonic acid group (-SO) appears 3 H) Characteristic absorption peak of (C) at 1216.0cm -1 The position shows a strong absorption peak, and the telescopic vibration absorption peak is attributed to phosphonic acid group P=0, 990cm -1 The absorption peak is the telescopic vibration absorption peak of ether-O-, 1203cm -1 And 1150cm -1 The two strongest absorptions are caused by CF vibration, 720cm -1 And 641cm -1 Characteristic peaks of (C) are attributed to-CF after tetrafluoroethylene copolymerization 2 CF 2 The above results fully demonstrate that the target product was successfully synthesized.
Example 2:
using the resin of example 1, a film-forming liquid was prepared with N, N-dimethylacetamide, and then the film-forming liquid was coated on a polytetrafluoroethylene-reinforced net (2 layers, porosity 80%, grammage 3.2 g/m) by a wire rod 2 ). And heating the solvent to volatilize and form a film to obtain the polymeric phosphonic acid ionic film with the thickness of 12 mu m.
The remaining components and preparation methods were the same as in example 1.
Example 3:
the resin of example 1 was used to prepare a film-forming liquid, N-dimethylacetamide was used to prepare a film-forming liquid, 1wt% of an auxiliary agent A and 1wt% of an auxiliary agent B were added to the film-forming liquid, and the film-forming liquid having a solid content of 23% was obtained by stirring and dispersing uniformly, and coated on a polytetrafluoroethylene-reinforced net (2 layers, porosity 80%, gram weight 3.2 g/m) by means of a wire rod 2 ). And heating the solvent to volatilize and form a film to obtain the polymeric phosphonic acid ionic film with the thickness of 12 mu m.
The other components and preparation methods are the same as in example 2.
Example 4:
in this example, tetrafluoroethylene monomer was replaced with chlorotrifluoroethylene to give a polymeric phosphonic acid resin. A13 μm polymeric phosphonic acid ion membrane was prepared using the procedure of example 3.
The remaining components and preparation method were the same as in example 1.
Wherein the ion exchange capacity of the prepared polymerized phosphonic acid resin is 1.6mmol/g, the number average molecular weight is 41 ten thousand, the polymer structure contains 43.5 percent of tetrafluoroethylene polymerization units, 20.6 percent of perfluorovinyl ether phosphonate polymerization units, 20.4 percent of perfluorovinyl phosphonate polymerization units and 15.5 percent of perfluorosulfonyl fluoride vinyl ether polymerization units.
Example 5:
this example replaces the perfluorovinyl ether phosphonate monomer with (CF) 2 ＝CF-O-CF 2 CF 2 -P＝O-(OCH 3 ) 2 ). The remaining components and steps were the same as in example 1. The polymeric phosphonic acid resin is prepared.
The prepared polymeric phosphonic acid resin has the ion exchange capacity of 1.3mmol/g and the number average molecular weight of 42 ten thousand, the polymer structure contains 43.4 percent of tetrafluoroethylene polymerization units, 20.3 percent of perfluorovinyl ether phosphonate polymerization units, 20.7 percent of perfluorovinyl phosphonate polymerization units and 15.6 percent of perfluorosulfonyl fluoride vinyl ether polymerization units.
Dissolving the polymeric phosphonic acid resin in N, N-dimethylformamideTo the resulting dispersion, 1wt% of an auxiliary A and 1wt% of an auxiliary B were added, respectively. Stirring and dispersing uniformly to obtain film-forming liquid with solid content of 22%, coating the film-forming liquid on a polyethylene reinforced net (2 layers, porosity of 80% and gram weight of 3.2 g/m) through a wire rod 2 ) After heating, the solvent was volatilized to give a polymeric phosphonic acid ion membrane of 12 μm.
Wherein R in ligand L in auxiliary agent A 1 ，R 4 Is C 6 H 5 ，R 2 Is OH, R 3 Is H;
the metal M is Ce 2 (CO 3 ) 3 ·xH 2 O；
The ligand L and Ce 3+ The molar ratio of (2) is 4:1;
r in the auxiliary B 11 ，R 22 Is OCH 3 ；R 33 ，R 44 H.
Example 6:
the polymerized phosphonic acid precursor polymer obtained in example 1 was melt extruded into a film by means of a twin-screw extruder at 270℃and subsequently a continuous vacuum compounding process was used to form a two-layer polytetrafluoroethylene reinforced web (porosity 82%, grammage 3.0 g/m) 2 ) Is arranged inside to obtain a reinforced composite base film with a thickness of 150 mu m, and then sequentially passes through a sodium hydroxide solution with a mass percentage concentration of 30% at 80 ℃ and a sulfuric acid solution with a mass percentage concentration of 30% at 30 ℃ (H 2 SO 4 ) A flowing deionized water washing tank. The retention time of the reinforced composite base film in a sodium hydroxide solution is 30min, the retention time of the reinforced composite base film in a sulfuric acid solution is 30min, the reinforced composite base film is rinsed for 10min by deionized water in a deionized water tank, and sulfonyl fluoride (-SO) is contained in a precursor film 2 F) The side groups being converted to sulphonate ions (-SO) 3 H) Form (-PO (OR) in phosphonate ester 2 ) The side groups being converted to phosphonites (-PO) 3 H 2 ) And (3) in the form, hydrolyzing and acidifying to obtain the 15-mu m enhanced phosphonic acid sulfonic acid composite proton exchange membrane.
Example 7:
a film-forming liquid was prepared using the resin of example 5, except that in this example, the polytetrafluoroethylene reinforcing mesh was 3 layers, the porosity was 82%, and the grammage was 3.0g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the R in ligand L in A 1 ，R 3 ,R 4 Is H, R 2 OH;
the remaining components and steps were the same as in example 5.
Comparative example 1
Using perfluorovinyl ether sulfonyl fluoride monomer CF 2 ＝CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -SO 2 F and tetrafluoroethylene are copolymerized to prepare perfluorinated sulfonic acid resin, and the rest components, the content and the preparation method are the same as those of the example 1.
The ion exchange capacity of the prepared perfluorinated sulfonic acid resin is 1.1mmol/g, and the GPC test molecular weight number average molecular weight is 36 ten thousand.
Comparative example 2
The membrane of comparative example 1 was immersed in a phosphoric acid solution to obtain a phosphoric acid-doped perfluorosulfonic acid proton membrane, the molar ratio of doped phosphoric acid was 40%, and the exchange capacity was 1.2mmol/g.
Comparative example 3
50g of perfluorovinyl ether phosphonate monomer (CF) was added to the reaction vessel 2 ＝CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -P＝O-(OCH 3 ) 2 ) 150g of perfluorovinyl ether sulfonyl fluoride monomer (CF) 2 ＝CF-O-CF 2 CF 2 -SO 2 F) Polymerization was carried out with the remainder of the components and procedure as in example 1.
The ion exchange capacity of the prepared polymerized phosphonic acid resin is 1.3mmol/g, the number average molecular weight is 37 ten thousand, the polymer structure contains 60.5 mol percent of tetrafluoroethylene polymerization units, 20.5 mol percent of perfluorovinyl ether phosphonate polymerization units and 19.0 mol percent of perfluorosulfonyl fluoride vinyl ether polymerization units.
Comparative example 4
A sulphonic acid film of model NRE211 from dupont.
The results of the sample testing are summarized in Table 1.
The testing method of the ion exchange capacity, the tensile strength, the dimensional change rate, the conductivity and the fluoride ion release rate comprises the following steps:
ion exchange capacity: accurately weighing a certain weight of dry target product, treating in 80 ℃ water bath with Fenton reagent for 1h, performing ion exchange with NaCl aqueous solution with concentration of about 1M for more than 12h, collecting ion exchanged solution, titrating with 0.1M NaOH standard solution with phenolphthalein as indicator until the solution turns pink, wherein the Ion Exchange Capacity (IEC) value of the target product can be calculated according to the following formula:
IEC＝(V NaOH ×C NaOH )/m
wherein:
V NaOH the volume of the NaOH standard solution consumed, mL,
C NaOH the molar concentration of NaOH standard solution, mmol/mL,
m-mass of dry target product, g.
Tensile strength: GB/T1040-92.
Dimensional change rate: GB/T20042.3-2009.
Conductivity: the resistance R of the sample is tested by adopting a two-electrode method, an instrument is adopted as an electrochemical workstation Autolab PGSTA302, the frequency interval is 106Hz-10Hz, and the conductivity is calculated by a calculation formula:
σ＝L/RS
wherein:
l is the thickness (cm) of the membrane,
r is the resistance (q) of the diaphragm,
σ is the conductivity (S/cm) of the sample,
s is the area of the test portion (cm) 2 )；
The test temperatures were 120℃and 150℃respectively.
Fluoride ion release rate: 80ppm of Fe was added to 100mL of 30wt% hydrogen peroxide solution 2+ Ion, 0.2g of the fuel cell proton exchange membrane was carefully weighed and placed therein, and after 8 hours of holding at 80 ℃, a sample was taken from the solution. Washed with deionized water, dried at 80 ℃ for 2h, and weighed. Calculation of weight loss and determination of F in solution - Is contained in the composition.
Table 1 shows proton membrane performance data for examples 1-7 and comparative examples 1-4
Regarding the conductivity: as can be seen from Table 1, the polymeric phosphonic acid resin exchange membranes of examples 1-7 still maintain high conductivities of greater than 60mS/cm at 150℃far greater than the perfluorosulfonic acid proton exchange membrane, the phosphonic acid doped perfluorosulfonic acid proton membrane, the phosphonic acid-sulfonic acid crosslinked membrane obtained in comparative example 3, and the DuPont NRE211 sulfonic acid membrane, while the conductivities of the polymeric phosphonic acid resin exchange membranes provided in examples 1-7 were slightly reduced at room temperature, stable operation at room temperature was ensured. The invention adopts the polymerization type phosphonic acid resin composed of the perfluorovinyl phosphonic acid polymerization unit, the perfluorovinyl ether phosphonic acid polymerization unit and the perfluorovinyl ether sulfonic acid polymerization unit as the matrix of the polymerization type phosphonic acid membrane, and the three polymerization monomers are cooperated to improve the proton conductivity of the proton membrane under the high temperature condition, and simultaneously ensure the stable operation under the low temperature condition, thus obtaining the proton exchange membrane operated in a wide temperature range.
Regarding the tensile strength of the proton membrane: as can be seen from Table 1, examples 1-7 all had higher tensile strength than comparative examples 1-3, and example 1 did not have reinforcing net added, and the tensile strength was somewhat lower, but also higher than comparative examples 1-3, because of the stronger intermolecular forces between the long and short chain side groups, and the mechanical strength was enhanced.
Regarding the stability of proton membranes: as can be seen from Table 1, the fluoride ion release rates of examples 1-7 were much lower than those of comparative examples 1-3, mainly because the long and short chain side groups act synergistically to attenuate radical attack on the ionic membrane.
Claims (17)
1. A polymeric phosphonic acid ion membrane comprising a polymeric phosphonic acid resin;
the polymerized phosphonic acid resin is obtained by four-component copolymerization of fluoroolefin monomer, perfluorovinyl ether phosphonate monomer, perfluorovinyl phosphonate monomer and perfluorosulfonyl fluoride vinyl ether monomer to obtain polymerized phosphonic acid precursor polymer, and then hydrolyzing and acidifying, wherein the polymerized phosphonic acid resin has the structural formula:
；
wherein k is an integer of 0 to 3, f is an integer of 1 to 4, g is an integer of 0 to 4, t is an integer of 0 to 3, v is an integer of 1 to 4, a, b and c are integers of 1 to 20, a ', b ' and c ' are integers of 1 to 3, and R is- (OCF) 2 ) m (CF 2 ) n X, X is Cl or F; m and n are integers of 0 to 3; x/(x+y+z) =0.2-0.7, y/(x+y+z) =0.2-0.79, and z/(x+y+z) =0.01-0.1.
2. The polymeric phosphonic acid ion membrane of claim 1 characterized by a conductivity of not less than 60mS/cm at 150 ℃.
3. The polymeric phosphonic acid ionic membrane of claim 1 further comprising a porous fiber reinforcement and/or an adjunct.
4. A polymeric phosphonic acid ionic membrane according to any of claims 1-3, wherein k = 0-1, f = 2, g = 2, t = 0-1, v = 2 in the polymeric phosphonic acid resin structural formula.
5. The polymeric phosphonic acid ionic membrane of claim 4, wherein the polymeric phosphonic acid resin has an ion exchange capacity of 0.5 to 2.5mmol/g.
6. The polymeric phosphonic acid ionic membrane of claim 5, characterized in that the polymeric phosphonic acid resin has an ion exchange capacity of 0.9-1.6 mmol/g.
7. The polymeric phosphonic acid ionic membrane of claim 6, characterized in that the polymeric phosphonic acid resin has an ion exchange capacity of 1.0-1.4 mmol/g.
8. A polymeric phosphonic acid ionic membrane according to claim 3, wherein the auxiliary comprises an auxiliary (a) and/or an auxiliary (B);
wherein the auxiliary agent (A) is a metal complex formed by metal (M) and ligand (L), and the molar ratio of the metal (M) to the ligand (L) is 1:1-1:10;
the structural formula of the ligand (L) in the auxiliary agent (A) is as follows:
；
wherein R is 1 ，R 2 ，R 3 ，R 4 Is H, OH, CH 3 (CH 2 ) n1 O，CH 3 (CH 2 ) n1 ，NH 2 ，CH 2 OH，C 6 H 5 ，CF 3 (CF 2 ) n1 ，CF 3 (CF 2 ) n One or more of O, wherein n1 is an integer from 0 to 10;
the metal (M) is selected from the group consisting of a metal, a metal oxide, a metal salt, and any combination thereof;
the structural formula of the auxiliary agent (B) is as follows:
；
wherein R is 11 ，R 22 ，R 33 ，R 44 Is H, OH, CH 3 (CH 2 ) n2 O，CH 3 (CH 2 ) n2 ，NH 2 ，CH 2 OH，C 6 H 5 ，CF 3 (CF 2 ) n2 ，CF 3 (CF 2 ) n2 O, wherein n2 is an integer from 0 to 10.
9. The polymeric phosphonic acid ionic membrane of claim 8 wherein the molar ratio of metal (M) to ligand (L) is 1:1 to 1:5.
10. The polymeric phosphonic acid ion membrane of claim 8 wherein the polymeric phosphonic acid ion membrane comprises the following components:
the content of the polymeric phosphonic acid resin is 90-99.9 wt%, the content of the auxiliary agent is 0.1-10 wt%, the content of the auxiliary agent (A) is 0.05-5 wt%, and the content of the auxiliary agent (B) is 0.05-5 wt%.
11. The polymeric phosphonic acid ionic membrane of claim 10, wherein the polymeric phosphonic acid resin is 95-99.9 wt% and the auxiliary agent is 0.1-5 wt%; wherein the content of the auxiliary agent (A) is 0.05-3 wt%, and the content of the auxiliary agent (B) is 0.05-2 wt%.
12. A polymeric phosphonic acid ionic membrane according to claim 3, wherein the porous fibrous reinforcement is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene.
13. The polymeric phosphonic acid ionic membrane of claim 12, wherein the number of layers of porous fibrous reinforcement is 1-10.
14. The polymeric phosphonic acid ionic membrane of claim 13, wherein the number of layers of porous fibrous reinforcement is 1-5.
15. A method of preparing a polymeric phosphonic acid ionic membrane according to claim 1, comprising a melt extrusion process or a solution coating process;
the melt extrusion process is specifically as follows:
s1: preparing a base film from a polymerized phosphonic acid precursor polymer by adopting a double-screw extruder, and then placing a reinforcing layer on the surface or inside of the base film by adopting a continuous vacuum compounding process to prepare a reinforced composite base film;
s2: soaking the reinforced composite base film obtained in the step S1 in an alkali metal hydroxide solution, hydrolyzing and transforming, soaking in an acid solution, and washing with deionized water to obtain a final polymerized phosphonic acid ionic film;
wherein, the alkali metal hydroxide in the step S2 is KOH or NaOH aqueous solution; the acid solution is nitric acid, sulfuric acid, hydrochloric acid or a mixed solution thereof;
the specific steps of the solution coating process are as follows:
dissolving a polymerized phosphonic acid precursor polymer in a solvent, adding an auxiliary agent to disperse to prepare a film-making liquid, then taking glass or a porous fiber reinforced material as a substrate to form a film, and heating to volatilize the solvent to prepare a polymerized phosphonic acid ionic film;
wherein the film forming mode comprises the following steps: solution casting, wire rod coating, doctor blade coating, spraying or dipping; the solid content of the film-making liquid is 5-35 wt%; the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone, butanone, 1-5 carbon chain alcohol aqueous solution, formic acid or acetic acid.
16. The method for preparing the polymeric phosphonic acid ionic membrane according to claim 15, wherein the thickness of the polymeric phosphonic acid ionic membrane is 8-150 [ mu ] m.
17. The method for preparing the polymeric phosphonic acid ionic membrane according to claim 16, wherein the thickness of the polymeric phosphonic acid ionic membrane is 8-50 mu m.
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| CN202410033647.8A Pending CN117866132A (en) | 2021-10-18 | 2022-10-18 | Fluorine-containing resin dispersion liquid and preparation method and application thereof |
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| CN202211272307.8A Pending CN115991828A (en) | 2021-10-18 | 2022-10-18 | Perfluorinated sulfonic acid resins containing phosphonic acid structural units |
| CN202211272339.8A Active CN115991831B (en) | 2021-10-18 | 2022-10-18 | Fluorine-containing resin containing cyclic structure and preparation method thereof |
| CN202410035282.2A Pending CN117866133A (en) | 2021-10-18 | 2022-10-18 | Perfluorinated sulfonic acid resin dispersion containing phosphonic acid structural units, and preparation method and application thereof |
| CN202211272292.5A Pending CN115991827A (en) | 2021-10-18 | 2022-10-18 | Multi-copolymer containing sulfonyl fluoride, ion exchange resin and preparation method |
| CN202211272342.XA Active CN115991832B (en) | 2021-10-18 | 2022-10-18 | Mixed fluorine-containing ion resin |
| CN202211272321.8A Active CN115991830B (en) | 2021-10-18 | 2022-10-18 | High temperature resistant functional polymer |
| CN202311634040.7A Pending CN117700598A (en) | 2021-10-18 | 2022-10-18 | Fluorine-containing resin dispersion liquid containing cyclic structure and preparation method thereof |
| CN202211276230.1A Active CN115991835B (en) | 2021-10-18 | 2022-10-18 | Wide-temperature-zone polymerized phosphonic acid resin and preparation method thereof |
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