CN113801352B - Anion exchange membrane and preparation method and application thereof - Google Patents
Anion exchange membrane and preparation method and application thereof Download PDFInfo
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- CN113801352B CN113801352B CN202111093494.9A CN202111093494A CN113801352B CN 113801352 B CN113801352 B CN 113801352B CN 202111093494 A CN202111093494 A CN 202111093494A CN 113801352 B CN113801352 B CN 113801352B
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- anion exchange
- exchange membrane
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000007306 functionalization reaction Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000007790 scraping Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000003190 augmentative effect Effects 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NUUUANNAZVEWHM-UHFFFAOYSA-N 1,2-dibromohexane Chemical compound CCCCC(Br)CBr NUUUANNAZVEWHM-UHFFFAOYSA-N 0.000 claims description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 3
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 2
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 claims description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 2
- SLENBUXIYVBBQM-UHFFFAOYSA-N 1,7-dibromooctane Chemical compound BrCCCCCCC(C)Br SLENBUXIYVBBQM-UHFFFAOYSA-N 0.000 claims description 2
- AIVHUYXLPYIHJE-UHFFFAOYSA-N 1,8-dibromononane Chemical compound BrCCCCCCCC(C)Br AIVHUYXLPYIHJE-UHFFFAOYSA-N 0.000 claims description 2
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 239000012528 membrane Substances 0.000 abstract description 37
- 150000002500 ions Chemical class 0.000 abstract description 14
- 230000008961 swelling Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 18
- 238000005342 ion exchange Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- KKKDZZRICRFGSD-UHFFFAOYSA-O 3-benzyl-1h-imidazol-3-ium Chemical class C1=C[NH+]=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-O 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000004693 Polybenzimidazole Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920002480 polybenzimidazole Polymers 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229930184652 p-Terphenyl Natural products 0.000 description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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- 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
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/122—Copolymers statistical
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C08G2261/51—Charge transport
- C08G2261/516—Charge transport ion-conductive
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- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- H01M2300/00—Electrolytes
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides an anion exchange membrane and a preparation method and application thereof. The invention not only can promote the ion conduction capacity of the membrane, but also limits the swelling of the membrane and improves the mechanical strength of the membrane.
Description
Technical Field
The invention belongs to the technical field of anion exchange membranes, and relates to an anion exchange membrane, a preparation method and application thereof.
Background
To improve the ion-conducting capacity of the anion-exchange membrane, reduce the ohmic resistance, and improve the working efficiency of the electrochemical device, this objective is generally achieved by adopting a method of increasing the ion-exchange capacity (IEC) of the membrane material. However, this operation inevitably leads to an increase in the water absorption of the membrane material, an increase in swelling, a serious decrease in mechanical properties, an influence on the durability thereof in practical use, and a limitation in development thereof.
The existing anion exchange membrane mainly comprises different polymer skeleton grafted cationic groups, wherein the cationic groups are mainly quaternary ammonium groups, and a certain degree of contradiction exists between the ion exchange capacity and the mechanical strength of the anion exchange membrane, for example, when the water content is too high due to the overlarge ion exchange capacity, the membrane is easy to embrittle, and when the ion exchange capacity is too small, the mechanical strength of the membrane is ensured, but the ionic conductivity is greatly reduced. In addition, quaternized polymeric anion-exchange membranes may be subjected to OH under strong alkaline and high temperature conditions - The nucleophilic attack of (2) causes the quaternary ammonium groups to break away from the backbone, thereby causing chemical degradation of the membrane and a decrease in electrical conductivity and mechanical strength.
CN105566665a discloses a preparation method of a blending cross-linking anion exchange membrane, which uses vinyl imidazole monomer as raw material, firstly prepares polyvinyl imidazole by using free radical polymerization method, then uses benzyl bromide as quaternizing agent to react with polyvinyl imidazole to prepare brominated polyvinyl benzyl imidazolium salt, then the brominated polyvinyl benzyl imidazolium salt is blended with side amino polybenzimidazole in solution, uses epoxy resin as cross-linking agent to obtain brominated polyvinyl benzyl imidazolium salt/polybenzimidazole blending cross-linking anion exchange membrane; immersing the brominated polyvinyl benzyl imidazolium salt/polybenzimidazole blending crosslinking anion exchange membrane in an alkali solution, taking out the membrane, and washing the membrane to be neutral to obtain the hydrogenated polyvinyl benzyl imidazolium salt/polybenzimidazole blending crosslinking anion exchange membrane. The strength of the anion exchange membrane is poor.
CN110845849a discloses a preparation method of a non-crosslinked anion exchange membrane, which comprises the following steps: mixing an original polymer with an organic solvent, adding stannic chloride and a chloromethyl reagent, and reacting to obtain a chloromethylated polymer; aminating the chloromethylated polymer to obtain an aminated polymer; mixing the aminated polymer and the original polymer in an organic solvent, and casting the obtained polymer blend solution on a matrix to obtain the non-crosslinked anion exchange membrane. The anion exchange membrane has poor ion conductivity.
The above solution has a problem of poor membrane strength or poor ion conductivity, and therefore, it is necessary to develop an anion exchange membrane having both good ion conductivity and good strength.
Disclosure of Invention
The invention aims to provide an anion exchange membrane and a preparation method and application thereof. I.e. at the same time as the ion exchange sites, a cross-linked network is introduced. The invention not only can promote the ion conduction capacity of the membrane, but also limits the swelling of the membrane and improves the mechanical strength of the membrane.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an anion exchange membrane comprising a cross-linked anion exchange membrane having a structural formula as shown in formula I:
wherein n is 2 to 8, for example: 2. 3, 4, 5, 6, 7 or 8,x is the molar ratio of the crosslinked portion in the crosslinked anion exchange membrane, y is the molar ratio of the uncrosslinked portion in the crosslinked anion exchange membrane, x is 10 to 60%, for example: 10%, 20%, 30%, 40%, 50% or 60%, etc., y is 40 to 90%, for example: 40%, 50%, 60%, 70%, 80% or 90%, etc., AR 1 AR (augmented reality) 2 Is an aryl monomer.
The anion exchange membrane disclosed by the invention is crosslinked and simultaneously quaternized to the polymer, so that the ion conduction capability of the material is ensured, the swelling of the membrane material is restrained by introducing a crosslinked structure, the tolerance of the membrane material in a water system and an organic system is improved, the membrane material has excellent ion conduction capability, and the membrane material has excellent mechanical property due to the construction of a crosslinked network, and meanwhile, the tolerance of the membrane material in an organic solvent and an alcohol solvent is greatly improved.
Preferably, the anion exchange membrane comprises a polymer having a structural formula as shown in formula II:
a is the molar proportion of crosslinked moieties in the polymer, b is the molar proportion of uncrosslinked moieties in the polymer, a is from 10 to 60%, for example: 10%, 20%, 30%, 40%, 50% or 60%, etc., y is 40 to 90%, b is 40 to 90%, for example: 40%, 50%, 60%, 70%, 80% or 90%, etc., AR 1 AR (augmented reality) 2 Is an aryl monomer.
According to the anion exchange membrane disclosed by the invention, a part of uncrosslinked polymer can be reserved in the crosslinked anion exchange membrane according to the requirement, so that the semi-interpenetrating anion exchange membrane is obtained, and the semi-interpenetrating anion exchange membrane consists of a movable ion transfer chain segment and a crosslinked chain segment which provides mechanical strength and inhibits swelling, so that compared with the pure crosslinking, the ion transfer in the membrane is inhibited, and the brittleness of the membrane is increased. The semi-interpenetrating network provides a connected ion channel and inhibits membrane brittleness.
Preferably, the aryl-based monomer comprises any one or a combination of at least two of biphenyl, p-terphenyl, m-terphenyl, tetra-biphenyl, diphenylmethane or 9, 9-dimethylfluorene.
In a second aspect, the present invention provides a process for the preparation of an anion exchange membrane according to the first aspect, the process comprising the steps of:
(1) Mixing aryl monomers and N-methyl-4-piperidone with a first solvent, adding trifluoromethanesulfonic acid for hydroxyalkylation reaction to obtain a polymer, mixing the polymer with a second solvent, and adding a first precipitant to obtain a precursor;
(2) Mixing the precursor obtained in the step (1) with a third solvent, adding methyl iodide for functionalization, adding a second precipitator, mixing the obtained precipitate with a fourth solvent to obtain a mixed solution, adding a cross-linking agent for cross-linking, carrying out film scraping treatment on the obtained solution, and drying at a high temperature to obtain the anion exchange membrane.
According to the invention, the membrane material is quaternized, and simultaneously in-situ crosslinking is realized, namely, the ion exchange sites are introduced, and a crosslinking network is also introduced, so that the water absorption capacity of the membrane material can be reduced to a certain extent, further the swelling of the membrane material is inhibited, the reduction of the ion exchange sites can be avoided, the transfer of ions in the membrane is limited, and the mechanical property of the prepared anion exchange membrane is improved.
Preferably, the molar ratio of the aryl-based monomer and N-methyl-4-piperidone in step (1) is 1 (1-1.5), for example: 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5, etc.
Preferably, the molar ratio of the trifluoromethanesulfonic acid to the N-methyl-4-piperidone is (1-2): 1.
Preferably, the first solvent comprises any one or a combination of at least two of dichloromethane, chloroform or tetrahydrofuran.
Preferably, the hydroxyalkylation reaction is carried out in an ice-water bath.
Preferably, the time of the hydroxyalkylation reaction is 2 to 8 hours, for example: 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc.
Preferably, the second solvent of step (1) comprises any one or a combination of at least two of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide.
Preferably, the first precipitant comprises any one or a combination of at least two of ethyl acetate, water, ethanol, diethyl ether, tetrahydrofuran or acetone.
Preferably, the third solvent of step (2) comprises any one or a combination of at least two of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide.
Preferably, the molar ratio of the precursor to methyl iodide is 1 (0.2 to 0.6), for example: 1:0.2, 1:0.3, 1:0.4, 1:0.5, or 1:0.6, etc.
Preferably, the temperature of the functionalization is 60-80 ℃, for example: 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃ and the like.
Preferably, the time of the functionalization is 5 to 8 hours, for example: 5h, 6h, 7h or 8h, etc.
Preferably, the second precipitant of step (2) comprises any one or a combination of at least two of aqueous sodium carbonate, aqueous potassium carbonate, aqueous sodium hydroxide or aqueous potassium hydroxide.
The third solvent comprises any one or a combination of at least two of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide.
Preferably, the cross-linking agent is added prior to the impurity removal treatment.
Preferably, the mass concentration of the mixed solution is 5 to 20wt%, for example: 5wt%, 8wt%, 10wt%, 15wt% or 20wt%, etc.
Preferably, the cross-linking agent comprises any one or a combination of at least two of 1, 2-dibromohexane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 7-dibromooctane or 1, 8-dibromononane.
Preferably, the molar ratio of the precursor and the crosslinking agent is 1 (0.2 to 0.4), for example: 1:0.2, 1:0.3, 1:0.35, or 1:0.4, etc.
Preferably, the crosslinking temperature is 60 to 120 ℃, for example: 60 ℃, 80 ℃, 100 ℃ or 120 ℃ and the like.
Preferably, the temperature of the film scraping treatment in the step (2) is 60-120 ℃, for example: 60 ℃, 80 ℃, 100 ℃ or 120 ℃ and the like.
Preferably, the temperature of the high-temperature drying is 80-120 ℃, for example: 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ and the like.
In a third aspect, the present invention provides the use of an anion exchange membrane according to the first aspect in hydrogen-oxygen fuel cells, methanol fuel cells, alkaline polymer water electrolysis hydrogen production, metal-air cells, flow batteries, CO 2 Reduction or super capacitor.
Compared with the prior art, the invention has the following beneficial effects:
(1) The anion exchange membrane provided by the invention not only has excellent ion conduction capacity, but also has excellent mechanical properties due to the construction of a cross-linked network, and meanwhile, the tolerance of the membrane material in an organic solvent and an alcohol solvent is greatly improved.
(2) According to the invention, the membrane material is quaternized, and simultaneously in-situ crosslinking is realized, namely, the ion exchange sites are introduced, and a crosslinking network is also introduced, so that the water absorption capacity of the membrane material can be reduced to a certain extent, further the swelling of the membrane material is inhibited, the reduction of the ion exchange sites can be avoided, the transfer of ions in the membrane is limited, and the mechanical property of the prepared anion exchange membrane is improved.
Drawings
FIG. 1 is a graph showing the tensile strength properties of the anion exchange membranes described in example 1 and comparative example 1.
FIG. 2 is a graph comparing the conductivities of the anion exchange membranes described in example 1 and comparative example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present example provides an anion exchange membrane prepared by:
(1) 67.02g of p-terphenyl and 37.8mL of N-methyl-4-piperidone (the molar ratio is 1:1.2) are mixed with dichloromethane, 9mL of trifluoromethanesulfonic acid (the molar ratio of trifluoromethanesulfonic acid to N-methyl-4-piperidone is 1.5:1) is added for carrying out hydroxyalkylation reaction for 6 hours to obtain a polymer, the polymer is mixed with dimethyl sulfoxide, deionized water is added, and a precursor is obtained through filtration, washing and drying;
(2) Mixing 10g of the precursor obtained in the step (1) with dimethyl sulfoxide, adding 250 mu L of methyl iodide, performing functionalization for 6 hours at 70 ℃, adding sodium carbonate aqueous solution, mixing the obtained precipitate with dimethyl sulfoxide to obtain a mixed solution with the mass concentration of 10wt%, filtering, removing impurities, adding 310 mu L of 1, 2-dibromohexane, performing cross-linking at 80 ℃, pouring the obtained solution on an automatic film scraping machine, adjusting the height of a scraper according to actual requirements, scraping films with different thicknesses, drying at 100 ℃, and continuously drying for a period of time after film formation to obtain the anion exchange film.
Example 2
The present example provides an anion exchange membrane prepared by:
(1) 48.8g of diphenylmethane and 37.8mL of N-methyl-4-piperidone (the molar ratio is 1:1.2) are mixed with 9mL of dichloromethane, 9mL of trifluoromethanesulfonic acid (the molar ratio of trifluoromethanesulfonic acid to N-methyl-4-piperidone is 1.5:1) is added for carrying out hydroxyalkylation reaction for 6h to obtain a polymer, the polymer is mixed with N-methylpyrrolidone, diethyl ether is added, and the precursor is obtained through filtration, washing and drying;
(2) Mixing 10g of the precursor obtained in the step (1) with N-methylpyrrolidone, dividing into two parts, adding 1.2mL of methyl iodide into one part for functionalization for 6 hours at 80 ℃, adding 0.3mL of methyl iodide into the other part for functionalization for 40 minutes at 80 ℃, adding 0.8mL of 1, 3-dibromopropane for crosslinking at 80 ℃, mixing the obtained two solutions, filtering for impurity removal, and defoaming to obtain a mixed solution, pouring the obtained mixed solution on an automatic film scraping machine, regulating the height of a scraper according to actual requirements to scrape films with different thicknesses, drying at 100 ℃, and continuously drying for a period of time after film formation to obtain the anion exchange membrane.
Example 3
This example differs from example 1 only in that the crosslinking temperature in step (2) is 50℃and the other conditions and parameters are exactly the same as in example 1.
Example 4
This example differs from example 1 only in that the crosslinking temperature in step (2) is 100℃and the other conditions and parameters are exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the time for the crosslinking in step (2) is 1h, and other conditions and parameters are exactly the same as in example 1.
Example 6
The difference between this example and example 1 is that the time for crosslinking in step (2) is 3h, and the other conditions and parameters are exactly the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that no crosslinking treatment was performed, and other conditions and parameters were exactly the same as in example 1.
Performance test:
the anion exchange membranes obtained in examples 1 to 6 and comparative example 1 were subjected to tensile strength and conductivity tests, and the test results are shown in table 1:
TABLE 1
As can be seen from table 1, the present invention can prepare a crosslinked or semi-interpenetrating anion exchange membrane according to different performance requirements for the anion exchange membrane, as can be seen from a comparison of example 1 and example 2.
As can be seen from a comparison of examples 1 and examples 3-4, the temperature of the functionalization in step (2) affects the performance of the prepared anion exchange membrane, and if the crosslinking temperature is too low, the reaction activity is low, the reaction between the crosslinking agent and the active site is insufficient, the crosslinking effect is poor, the mechanical strength and the ion conductivity of the membrane material are affected, and if the crosslinking temperature is too high, the reaction activity is high, and the membrane becomes gel without forming a membrane.
As can be seen from the comparison of examples 1 and examples 5 to 6, the functionalization time in the step (2) affects the performance of the prepared anion exchange membrane, the functionalization time is controlled to be 5 to 8 hours, the prepared anion exchange membrane has excellent performance, if the crosslinking time is too short, the crosslinking reaction does not take place, the crosslinking fails, if the crosslinking time is too long, the crosslinking is sufficiently carried out, the gelation phenomenon occurs, and the membrane cannot be cast.
The tensile light performance comparison chart and the conductivity comparison chart of the anion exchange membranes of example 1 and comparative example 1 are shown in fig. 1-2, and as can be seen from fig. 1-2 in combination with table 1, the anion exchange membranes of the present invention have excellent ion conductivity, and the construction of the crosslinked network also enables the membrane material to have excellent mechanical properties, and meanwhile, the tolerance of the membrane material in organic solvents and alcohol solvents is greatly improved.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (23)
1. An anion exchange membrane, characterized in that the anion exchange membrane comprises a cross-linked anion exchange membrane, and the structural formula of the cross-linked anion exchange membrane is shown as formula I:
wherein n is 2 to 8,x, y is the molar ratio of the uncrosslinked portion in the crosslinked anion exchange membrane, x is 10 to 60%, y is 40 to 90%, and AR 1 AR (augmented reality) 2 Is aryl monomer;
the anion exchange membrane comprises a polymer, and the structural formula of the polymer is shown as formula II:
a is the molar proportion of crosslinked parts in the polymer, b is the molar proportion of uncrosslinked parts in the polymer, a is 10-60%, b is 40-90%, AR 3 AR (augmented reality) 4 Is aryl monomer;
the anion exchange membrane is prepared by the following method:
(1) Mixing aryl monomers and N-methyl-4-piperidone with a first solvent, adding trifluoromethanesulfonic acid for hydroxyalkylation reaction to obtain a polymer, mixing the polymer with a second solvent, and adding a first precipitant to obtain a precursor;
(2) Mixing the precursor obtained in the step (1) with a third solvent, dividing the mixture into two parts, adding methyl iodide into one part for functionalization, adding methyl iodide into the other part for functionalization, adding a second precipitant, mixing the obtained precipitate with a fourth solvent to obtain a mixed solution, adding a cross-linking agent for cross-linking, mixing the two solutions obtained in the first part and the second part, carrying out film scraping treatment on the mixed solution, and drying at a high temperature to obtain the anion exchange membrane.
2. The anion exchange membrane of claim 1, wherein the aryl-based monomer comprises any one or a combination of at least two of biphenyl, para-terphenyl, meta-terphenyl, tetra-biphenyl, diphenylmethane, or 9, 9-dimethylfluorene.
3. A process for preparing an anion exchange membrane according to claim 1 or 2, comprising the steps of:
(1) Mixing aryl monomers and N-methyl-4-piperidone with a first solvent, adding trifluoromethanesulfonic acid for hydroxyalkylation reaction to obtain a polymer, mixing the polymer with a second solvent, and adding a first precipitant to obtain a precursor;
(2) Mixing the precursor obtained in the step (1) with a third solvent, dividing the mixture into two parts, adding methyl iodide into one part for functionalization, adding methyl iodide into the other part for functionalization, adding a second precipitant, mixing the obtained precipitate with a fourth solvent to obtain a mixed solution, adding a cross-linking agent for cross-linking, mixing the two solutions obtained in the first part and the second part, carrying out film scraping treatment on the mixed solution, and drying at a high temperature to obtain the anion exchange membrane.
4. The process according to claim 3, wherein the molar ratio of the aryl-based monomer to N-methyl-4-piperidone in the step (1) is 1 (1-1.5).
5. A process according to claim 3, wherein the molar ratio of trifluoromethanesulfonic acid to N-methyl-4-piperidone is (1-2): 1.
6. The method of claim 3, wherein the first solvent comprises any one or a combination of at least two of dichloromethane, chloroform, or tetrahydrofuran.
7. A process according to claim 3, wherein the hydroxyalkylation is carried out in an ice-water bath.
8. The process according to claim 3, wherein the hydroxyalkylation is carried out for a period of 2 to 8 hours.
9. The method of claim 3, wherein the second solvent of step (1) comprises any one or a combination of at least two of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide, or N, N-dimethylacetamide.
10. The method of claim 3, wherein the first precipitant comprises any one or a combination of at least two of ethyl acetate, water, ethanol, diethyl ether, tetrahydrofuran, or acetone.
11. The method of claim 3, wherein the third solvent of step (2) comprises any one or a combination of at least two of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.
12. The method of claim 3, wherein the molar ratio of the precursor to methyl iodide is 1 (0.2 to 0.6).
13. A method of preparation as claimed in claim 3 wherein the functionalisation is carried out at a temperature of 60 to 80 ℃.
14. A method of preparation according to claim 3 wherein the time of functionalization is between 5 and 8 hours.
15. The method of claim 3, wherein the second precipitant of step (2) comprises any one or a combination of at least two of aqueous sodium carbonate, aqueous potassium carbonate, aqueous sodium hydroxide, or aqueous potassium hydroxide;
the third solvent comprises any one or a combination of at least two of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide.
16. A method of preparing as claimed in claim 3 wherein the cross-linking agent is preceded by a de-noising treatment.
17. The method according to claim 3, wherein the mass concentration of the mixed solution is 5 to 20wt%.
18. The method of claim 3, wherein the cross-linking agent comprises any one or a combination of at least two of 1, 2-dibromohexane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 7-dibromooctane, or 1, 8-dibromononane.
19. The method of claim 3, wherein the molar ratio of the precursor to the crosslinking agent is 1 (0.2 to 0.4).
20. A method of preparation according to claim 3 wherein the cross-linking is at a temperature of 60 to 120 ℃.
21. The method according to claim 3, wherein the temperature of the film-scraping treatment in the step (2) is 60 to 120 ℃.
22. The method according to claim 3, wherein the high temperature drying is performed at 80 to 120 ℃.
23. Use of an anion exchange membrane according to claim 1 or 2, wherein the anion exchange membrane is used in oxy-hydrogen fuel electrotechnologyPool, methanol fuel cell, alkaline polymer water electrolysis hydrogen production, metal-air cell, flow cell, CO 2 Reduction or super capacitor.
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