CN115948051A - Cross-linked alkaline anion exchange membrane and preparation method thereof - Google Patents
Cross-linked alkaline anion exchange membrane and preparation method thereof Download PDFInfo
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 88
- 150000004693 imidazolium salts Chemical class 0.000 claims abstract description 79
- 239000012528 membrane Substances 0.000 claims abstract description 55
- -1 polyethylene Polymers 0.000 claims abstract description 42
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 36
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005266 casting Methods 0.000 claims abstract description 28
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 28
- 239000004698 Polyethylene Substances 0.000 claims abstract description 19
- 229920000573 polyethylene Polymers 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 85
- 238000005303 weighing Methods 0.000 claims description 57
- 238000001035 drying Methods 0.000 claims description 42
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000002791 soaking Methods 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000013179 MIL-101(Fe) Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000013178 MIL-101(Cr) Substances 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000013206 MIL-53 Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000013174 zeolitic imidazolate framework-10 Substances 0.000 claims description 2
- 239000013171 zeolitic imidazolate framework-6 Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 13
- 239000000446 fuel Substances 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 7
- 239000003014 ion exchange membrane Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000008961 swelling Effects 0.000 abstract description 3
- 210000000170 cell membrane Anatomy 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- CJFFZVOOASEHPL-UHFFFAOYSA-O C(CCCCC)[N+]1=CNC(=C1C)C Chemical class C(CCCCC)[N+]1=CNC(=C1C)C CJFFZVOOASEHPL-UHFFFAOYSA-O 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 230000003113 alkalizing effect Effects 0.000 description 10
- RVZHVQZQEPMTQJ-UHFFFAOYSA-N ethanol;1h-imidazole Chemical compound CCO.C1=CNC=N1 RVZHVQZQEPMTQJ-UHFFFAOYSA-N 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 150000002460 imidazoles Chemical class 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CNIOVXUZRNOZNF-UHFFFAOYSA-O CC=1N(C=[NH+]C=1C)CCCC Chemical class CC=1N(C=[NH+]C=1C)CCCC CNIOVXUZRNOZNF-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical class CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 description 1
- YDZFQBFYDIPUGN-UHFFFAOYSA-O CCCCCC[N+]1=CNC(CC)=C1CC Chemical class CCCCCC[N+]1=CNC(CC)=C1CC YDZFQBFYDIPUGN-UHFFFAOYSA-O 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000003313 weakening effect 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
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the field of fuel cell membrane materials, and relates to a cross-linking type alkaline anion exchange membrane and a preparation method thereof. The alkaline anion exchange membrane is compounded by taking imidazolium salt crystals, polybenzimidazole and polyethylene derivatives as raw materials, wherein the imidazolium salt crystals are synthesized by fixing a substance formed by taking 4, 5-disubstituted imidazolium salt as a raw material in a metal organic framework crystal material by adopting a low-temperature vacuum method; the alkaline anion exchange membrane forms polymer solution by polybenzimidazole and polyethylene derivatives, the polymer solution is added into imidazolium salt crystals to obtain functionalized membrane casting solution, the prepared exchange membrane is soaked in ethanol solution of 4, 5-disubstituted imidazolium salt, and the high-conductivity cross-linked alkaline anion exchange membrane is obtained by alkalization. The ion exchange membrane has high stability, low swelling degree, high mechanical strength, high ion transfer characteristic and high chemical stability.
Description
Technical Field
The invention relates to a cross-linking type alkaline anion exchange membrane and a preparation method thereof, belonging to the field of fuel cell membrane materials.
Background
Under the situation that the current environmental problem is more and more severe, energy conservation and emission reduction are in the imperative situation, and the development and the utilization of efficient, clean and sustainable energy technology are more and more important. The alkaline Anion Exchange Membrane Fuel Cell (AEMFC) can be used as one of fuel cells, can be used as an energy device, and has the remarkable advantages of high energy conversion efficiency, high starting speed, high specific power, zero emission and the like. The method combines the advantages of proton exchange membrane fuel cells and alkaline fuel cells, not only adopts easily-packaged solid polymers as electrolytes, but also greatly improves the activity and stability of the catalyst under alkaline conditions compared with those under acidic conditions, and further gets rid of the dependence on noble metal catalysts such as platinum and the like, thereby providing a new hope for large-scale commercial application of the fuel cells.
As a core component of alkaline membrane fuel cells, the development of alkaline membranes (AEMs) has been a focus and difficulty of research in this field but such membranes suffer from the contradiction between ion exchange capacity and mechanical properties, as well as low ionic conductivity and poor chemical stability. The cross-linked structure can improve the dimensional stability of the membrane, but the conductivity loss is severe. The traditional alkaline membrane mainly adopts polyphenyl ether and polyaryletheraether macromolecules as framework materials. Currently, the key to the development of AEMFC is the development of alkaline membranes (AEMs), whose ionic conductivity and chemical stability are key parameters that determine the core parameters of fuel cell, such as output power, energy density and service life. Compared with Proton Exchange Membranes (PEM), AEMs conduct OH < - >, have larger OH < - > ionic radius than H < + >, and have the defect of low ionic conductivity and the like. On the other hand, since alkaline membranes are susceptible to chemical degradation, this is particularly the case where insufficient hydration of the membrane occurs. It can be seen from the above that the improvement of the ionic conductivity and chemical stability of AEMs is an important issue to be solved urgently.
The synthesis of novel cation to replace quaternary ammonium group has become a hotspot of recent research, imidazole is a five-membered ring with a pi conjugated structure as a cation functional group, and the resonance effect existing in the ring can weaken the density of electron cloud, thereby weakening OH - The stability is improved by the attack of (2), but the attack of (3) on different main chains shows distinct alkali-resistant stability. At present, the alkali resistance stability of imidazole functional groups is improved to a certain extent mainly through the substituent effects of C2, N1 and N3.
However, hugar et al found that N1 and C2 modified imidazoles alone still have the degradation problem, and when C4 and C5 positions on imidazole rings are substituted by substituents, the imidazoles can be stabilized in 5M KOH at 80 ℃ for more than 30 days, but currently, researches on AEMs of C4 and C5 substituted imidazoles are few, and the conductivity and battery discharge performance of AEMs using imidazoles as functional groups are generally very low, and the compatibility mechanism of such imidazoles and Pt-based catalysts is still deeply researched. Therefore, how to increase the number of functional groups and prevent the loss of functional groups becomes a critical issue that must be addressed, while ensuring high chemical stability of the imidazole AEMs.
Disclosure of Invention
The invention aims to provide a high-conductivity cross-linked alkaline anion-exchange membrane and a preparation method thereof, and aims to increase the number of functional groups and prevent the functional groups from losing while ensuring high chemical stability, so as to solve the problems of low conductivity and short service life of the alkaline anion-exchange membrane.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a basic anion exchange membrane, which is compounded by taking imidazolium salt crystals, polybenzimidazole and polyethylene derivatives as raw materials, wherein the imidazolium salt crystals are as follows: a substance formed by taking 4, 5-disubstituted imidazolium salt as a raw material is fixed in the metal organic framework crystal material; the 4, 5-disubstituted imidazolium salt is 1-butyl C4, C5 disubstituted imidazolium salt or 1-hexyl C4, C5 disubstituted imidazolium salt.
In the above technical solution, further, the raw material of the imidazolium salt crystal further includes p-chloromethyl styrene.
In the above technical solution, further, the metal organic framework crystal material is a cubic structure having micropores, and the pore diameter of the micropores is 100-1000nm; the metal organic framework crystal material is one or more than two of MIL-101 (Fe), MIL-101 (Cr), MIL-53 (Fe), ZIF-6, ZIF-8 and ZIF-10;
the polyethylene derivative is any one of poly-p-chloromethyl styrene and poly-p-chloromethyl-alpha-methyl styrene.
In the above technical solution, further, the imidazolium salt crystal is synthesized by a low temperature vacuum method, and 4, 5-disubstituted imidazolium salt reacts with other raw materials to be "fixed" in the crystal material of the metal-organic framework material having a microporous cubic structure, including the following steps:
(1) Placing the metal organic framework crystal material in a Schlenk tube with a constant-pressure funnel, and continuously vacuumizing to keep the metal organic framework crystal material in a vacuum state;
(2) Under a low-temperature environment, mixing a mixed solution of the 4, 5-disubstituted imidazolium salt and p-chloromethyl styrene with a metal organic framework crystal material, and stirring to react the 4, 5-disubstituted imidazolium salt and the p-chloromethyl styrene;
(3) After the reaction is finished, centrifugal treatment is carried out, and the precipitate is dried to carry out self-crosslinking on vinyl in the chloromethyl styrene to obtain the imidazolium salt crystal.
In the technical scheme, further, the vacuum degree of the vacuum state in the step (1) is-0.6 to-1.0 MPa; the low-temperature reaction temperature in the step (2) is-20 to-10 ℃, the stirring time is 48 to 96 hours, and the molar ratio of the metal organic framework crystal material, the 4, 5-disubstituted imidazolium salt and the chloromethyl styrene is 1; in the step (3), the drying temperature of the precipitate is 60-100 ℃, and the drying time is 4-8h; the steps (1) and (2) are in the same vacuum state.
In the above technical solution, further, the 1-butyl C4, C5 disubstituted imidazolium salt or 1-hexyl C4, C5 disubstituted imidazolium saltWherein the C4 and C5 substituents are R respectively 1 And R 2 Said R is 1 And R 2 All of methyl, ethyl, propyl, butyl, isopropyl and tert-butyl, and the structures of the 1-butyl C4, C5 disubstituted imidazolium salt or the 1-hexyl C4, C5 disubstituted imidazolium salt are respectively as follows:
the invention also provides a preparation method of the alkaline anion-exchange membrane, which comprises the following membrane preparation steps:
A. preparing a polybenzimidazole high-boiling-point solution, adding a polyethylene derivative at room temperature, and stirring to obtain a polybenzimidazole/polyethylene derivative mixed solution;
B. adding an imidazolium salt crystal into the mixed solution of the polybenzimidazole/polyethylene derivatives obtained in the step A, and stirring at room temperature to obtain a functionalized membrane casting solution;
C. pouring the casting solution prepared in the step B into a glass mold, and after the casting solution is fully dried, stripping the obtained film from the glass mold;
D. c, soaking the membrane obtained in the step C in an ethanol solution of 4, 5-disubstituted imidazolium salt, and then fishing out the membrane;
E. and D, soaking the membrane fished out in the step D in an alkaline solution, then washing the membrane for more than 5 times by using deionized water, and drying to obtain the high-conductivity cross-linked alkaline anion exchange membrane.
In the above technical solution, further, the preparation method of the polybenzimidazole high boiling point solution in step a comprises: weighing polybenzimidazole, adding the polybenzimidazole into a high boiling point solvent, and stirring until the polybenzimidazole is dissolved to obtain a polybenzimidazole high boiling point solution with the mass concentration of 0.5-2wt%, wherein the high boiling point solvent is one of N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide.
In the above technical scheme, further, the stirring time in the step a is 24-48h, and the stirring time in the step B is 24-48h, and the mixture is uniformly mixed.
In the above technical solution, further, in the steps a and B, the imidazolium salt crystal: polybenzimidazole: polyethylene derivative = 1-3.
In the above technical scheme, further, in the step C, the drying temperature of the casting solution is 60-80 ℃, and the drying time is 24-48h; the mass concentration of the ethanol solution of the 4, 5-disubstituted imidazolium salt in the step D is 1-5wt%, and the soaking time is 24-48h.
In the technical scheme, further, the alkaline solution in the step E is one of sodium hydroxide or potassium hydroxide, the concentration of the alkaline solution is 0.1-2mol/L, the soaking time is 24-48h, and the drying temperature is 50-60 ℃.
Advantageous effects
1. The anion exchange membrane comprises imidazolium salt crystals, polybenzimidazole and polyethylene derivatives. Firstly, the imidazolium salt crystal takes imidazolium salt and a metal-organic framework material as raw materials, the metal-organic framework crystal material and the imidazolium salt are taken as functional materials of an anion exchange membrane, a metal-organic framework in the metal-organic framework crystal material provides a containing place for vinyl compounds in the imidazolium salt and chloromethyl styrene, so that the prepared anion exchange membrane cannot cause chemical degradation of the ion membrane and loss of functional ion groups due to change of reaction environment, and on the other hand, because the lattice structure of the metal-organic framework crystal material is highly ordered, the imidazolium salt and other compounds with the ion transmission function can uniformly and orderly transmit ions, so that the continuity and stability of ion transmission are ensured, the ion transmission resistance is reduced, the ion transmission efficiency is improved, and the electrochemical performance is further improved;
polybenzimidazole and polyethylene derivatives which do not contain unstable end groups such as ether bonds and the like are the molecular framework of the anion exchange membrane, on one hand, the stability in an alkaline environment is better, on the other hand, the compatibility of polymers such as the polybenzimidazole and the polyethylene derivatives and metal organic framework crystal materials is good, and imidazolium salt crystals prepared by using the metal organic framework crystal materials can be uniformly dispersed in a solution formed by the polymers, so that the defects of agglomeration, uneven distribution and the like can not occur; on the other hand, the polybenzimidazole/polyethylene derivative forms a stable network structure under the covalent crosslinking action, has strong mechanical strength and corrosion resistance, and can effectively improve the stability of the ion exchange membrane and prevent the excessive swelling of the ion exchange membrane under the combined action of the polybenzimidazole/polyethylene derivative and a metal organic framework in a 'fixed' form so as to achieve the aims of improving and strengthening the ion transfer characteristic and the chemical stability of the membrane.
2. Because the imidazolium salt crystal is adopted in the anion exchange membrane, 1-butyl or 1-hexyl C4 and C5 disubstituted imidazolium salt is introduced into the anion exchange membrane through covalent crosslinking and a metal organic framework in a fixing mode, namely, after the imidazolium salt reacts with a vinyl compound in chloromethyl styrene, the molecular structure is enlarged, the aperture in the crystal structure is unchanged, at the moment, the imidazolium salt can be firmly fixed in the crystal structure of the metal organic framework, the loss phenomenon is further avoided, and the number of functional groups in the membrane is effectively increased; in addition, in the process of synthesizing the imidazolium salt crystal, a low-temperature vacuum mode is adopted, as p-chloromethyl styrene is an active compound, polymerization reaction can occur at a slightly high temperature, the stability of the p-chloromethyl styrene can be ensured at a low temperature, and deterioration caused by reaction can not occur, and secondly, the p-chloromethyl styrene and the imidazolium salt can be smoothly pressed into a crystal structure under the action of negative pressure under vacuum and then locked, so that the number of functional groups in a membrane is further ensured;
3. the invention adopts the prepared imidazolium salt crystal as an additive, so that the metal organic framework material can fix functional materials, on one hand, the loss of a single-component compound along with the use of a membrane is prevented, and simultaneously, a single component has no function of transmitting ions, and if the imidazolium salt and the organic framework material are respectively mixed and added, the effect of fixing and stably transmitting ions cannot be realized.
4. After preparing the anion exchange membrane, the invention adopts alkaline solution to soak the anion exchange membrane for alkalization and functionalization, aiming at replacing chloride ions and the like in the imidazolium salt structure with OH - So that the composite membrane is fully alkalized, and the catalyst is not poisoned by chloride ions in the using process.
Detailed Description
The present invention will be described in further detail below.
Example 1:
(1) Weighing 6.99g (0.01 mol) of MIL-101 (Fe) in a Schlenk tube equipped with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-hexyl-4, 5-dimethylimidazolium salt and 1.525g (0.01 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 96 hours to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethylstyrene are fully reacted;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 398g of N-methylpyrrolidone, then weighing 1g of poly (p-chloromethyl styrene), and fully stirring for 24h for dissolving;
(5) Weighing 0.67g of imidazolium salt crystal, adding into the step (4), and continuously keeping the temperature of 25 ℃ and stirring for 24 hours to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) for 48 hours at 60 ℃ in a glass mold, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 99g of ethanol to obtain 1% of an imidazolium salt ethanol solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24h, then taking out, washing off the alkali solution on the surface of the membrane by using deionized water, and completely drying for 48h at 50 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Example 2:
(1) Weighing 7.19g (0.01 mol) of MIL-101 (Cr) into a Schlenk tube with a constant-pressure funnel, continuously vacuumizing to keep the vacuum degree at-0.8 MPa, and reducing the temperature of the Schlenk tube to-15 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-hexyl-4, 5-diethylimidazolium salt and 1.525g (0.01 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 36h to ensure that the 1-hexyl-4, 5-ethylimidazolium salt and the p-chloromethylstyrene are fully reacted;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 80 ℃ for 6 hours to enable the vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 198g of N, N-dimethylformamide, then weighing 1.2g of poly-p-chloromethyl styrene, and fully stirring for 24 hours for dissolving;
(5) Weighing 1g of imidazolium salt crystal, adding into the step (4), and continuously keeping the temperature of 25 ℃ and stirring for 36h to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) for 36 hours at 70 ℃ in a glass mold, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 39g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 2.5 percent;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 36h, fishing out, repeatedly washing for 10 times by using deionized water, then soaking the membrane in 1mol/L sodium hydroxide solution, fully alkalizing for 36h, then taking out, washing off an alkali solution on the surface of the membrane by using the deionized water, and completely drying for 36 at 55 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Example 3:
(1) 2.3g (0.01 mol) of ZIF-8 is weighed and placed in a Schlenk tube with a constant pressure funnel, the vacuum degree is kept at-0.6 MPa by continuous vacuum pumping, and the temperature of the Schlenk tube is reduced to-20 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-butyl-4, 5-dimethylimidazolium salt and 1.525g (0.01 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 48h to ensure that the 1-butyl-4, 5-dimethylimidazolium salt and the p-chloromethylstyrene are fully reacted;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 100 ℃ for 4h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 4g of polybenzimidazole at 25 ℃ and dissolving in 196g of N, N-dimethylamide, then weighing 4g of poly-p-chloromethyl-alpha-methylstyrene, and fully stirring for 24h for dissolving;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and continuously keeping the temperature of 25 ℃ and stirring for 24 hours to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) for 48 hours at 60 ℃ in a glass mold, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 19g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 5%;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 48h, taking out, repeatedly washing for 10 times by using deionized water, then soaking in 2mol/L potassium hydroxide solution, fully alkalizing for 48h, then taking out, washing off alkali solution on the surface of the membrane by using deionized water, and completely drying for 24h at 60 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Example 4:
(1) Weighing 6.99g (0.01 mol) of MIL-101 (Fe) in a Schlenk tube equipped with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-hexyl-4, 5-dimethylimidazolium salt and 0.7625g (0.005 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 96h to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethylstyrene are fully reacted;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 398g of N-methylpyrrolidone, then weighing 1g of poly (p-chloromethyl styrene), and fully stirring for 24h for dissolving;
(5) Weighing 0.67g of imidazolium salt crystal, adding into the step (4), and continuously keeping the temperature of 25 ℃ and stirring for 24 hours to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) for 48 hours at 60 ℃ in a glass mold, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 99g of ethanol to obtain 1% imidazolium salt ethanol solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24h, then taking out, washing away alkali solution on the surface of the membrane by using deionized water, and completely drying for 48h at 50 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Example 5:
(1) Weighing 6.99g (0.01 mol) of MIL-101 (Fe) into a Schlenk tube with a constant-pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-hexyl-4, 5-dimethylimidazolium salt and 7.625g (0.05 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 96 hours to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethylstyrene are fully reacted;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 398g of N-methylpyrrolidone, then weighing 1g of poly (p-chloromethyl) styrene, and fully stirring for 24h for dissolving;
(5) Weighing 0.67g of imidazolium salt crystal, adding into the step (4), and continuously keeping the temperature of 25 ℃ and stirring for 24 hours to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) in a glass mold at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 99g of ethanol to obtain 1% imidazolium salt ethanol solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24h, then taking out, washing away alkali solution on the surface of the membrane by using deionized water, and completely drying for 48h at 50 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Comparative example 1:
(1) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 398g of N-methylpyrrolidone, then weighing 1g of poly (p-chloromethyl styrene), and fully stirring and dissolving to obtain a casting solution;
(2) Drying the casting solution obtained in the step (1) for 48 hours at 60 ℃ in a glass mold, and stripping the dried film from a glass plate for later use;
(3) Weighing 1.0g of imidazolium salt and adding into 99g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 1%;
(4) And (3) placing the membrane obtained in the step (2) in the solution prepared in the step (3), soaking for 24h, taking out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24h, then taking out, washing away alkali solution on the surface of the membrane by using deionized water, and completely drying for 48h at 50 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Comparative example 2:
(1) Weighing 6.99g (0.01 mol) of MIL-101 (Fe) in a Schlenk tube equipped with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-hexyl-4, 5-dimethylimidazolium salt and 1.525g (0.01 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 96 hours to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethylstyrene are fully reacted;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable the vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 398g of N-methylpyrrolidone, then weighing 0.67g of imidazolium salt crystal, adding into the step (4), and continuously keeping the temperature at 25 ℃ and stirring for 24 hours to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) in a glass mold at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 99g of ethanol to obtain 1% of an imidazolium salt ethanol solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24h, then taking out, washing away alkali solution on the surface of the membrane by using deionized water, and completely drying for 48h at 50 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Comparative example 3:
(1) Weighing 6.99g (0.01 mol) of MIL-101 (Fe) in a Schlenk tube equipped with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 1.52 (0.01 mol) of 1-hexyl-4, 5-dimethylimidazolium salt and 1.525g (0.01 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 96h to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethylstyrene fully react;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 398g of N-methylpyrrolidone, then weighing 1g of poly (p-chloromethyl) styrene, and fully stirring and dissolving;
(5) Weighing 0.67g of imidazolium salt crystal, adding into the step (4), and continuously keeping the temperature of 25 ℃ and stirring for 24 hours to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) for 48 hours at 60 ℃ in a glass mold, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 99g of ethanol to obtain 1% imidazolium salt ethanol solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24h, then taking out, washing off the alkali solution on the surface of the membrane by using deionized water, and completely drying for 48h at 50 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Comparative example 4:
(1) Weighing 6.99g (0.01 mol) of MIL-101 (Fe) into a Schlenk tube with a constant-pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 4.56 (0.03 mol) of 1-hexyl-4, 5-dimethylimidazolium salt and 1.525g (0.01 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 96h to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethylstyrene fully react;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 398g of N-methylpyrrolidone, then weighing 1g of poly (p-chloromethyl styrene), and fully stirring and dissolving;
(5) Weighing 0.67g of imidazolium salt crystal, adding into the step (4), continuously keeping the temperature at 25 ℃, and stirring for 24 hours to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) for 48 hours at 60 ℃ in a glass mold, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 99g of ethanol to obtain 1% imidazolium salt ethanol solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24h, then taking out, washing away alkali solution on the surface of the membrane by using deionized water, and completely drying for 48h at 50 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
Comparative example 5:
(1) Weighing 6.99g (0.01 mol) of MIL-101 (Fe) in a Schlenk tube equipped with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-hexyl-4, 5-dimethylimidazolium salt and 0.38125g (0.0025 mol) of p-chloromethylstyrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 96h to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethylstyrene are fully reacted;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 2g of polybenzimidazole at 25 ℃, dissolving in 398g of N-methylpyrrolidone, then weighing 1g of poly (p-chloromethyl styrene), and fully stirring and dissolving;
(5) Weighing 0.67g of imidazolium salt crystal, adding into the step (4), and continuously keeping the temperature of 25 ℃ and stirring for 24 hours to obtain a casting solution;
(6) Drying the casting solution obtained in the step (5) in a glass mold at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystal prepared in the step (3) and adding the imidazolium salt crystal into 99g of ethanol to obtain 1% imidazolium salt ethanol solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24h, then taking out, washing away alkali solution on the surface of the membrane by using deionized water, and completely drying for 48h at 50 ℃ to obtain the high-conductivity cross-linked alkaline anion-exchange membrane.
In comparison with examples 1 to 5, no imidazolium salt crystals were added in comparative example 1, no polyethylene derivative was added in comparative example 2, and excessive or small amounts of imidazolium salt and p-chloromethylstyrene were added in comparative examples 3 to 6, respectively. The basic anion-exchange membranes of the examples and comparative examples were subjected to the tests of conductivity and tensile strength in duplicate, and the results are shown in table 1. Table 1 shows that the membrane prepared by the present invention has high conductivity and tensile strength, and the effect is superior to that of the comparative example. The imidazolium salt is respectively introduced into AEMs in two forms of covalent crosslinking and metal organic framework fixation, so that the number of functional groups in the membrane is increased, a regular ordered ion transfer channel is constructed by virtue of a regular lattice structure, and the ion transfer resistance is reduced; meanwhile, polybenzimidazole/polyvinyl benzyl chloride is used as a molecular skeleton, and the stability of the ion exchange membrane is improved and the excessive swelling of the ion exchange membrane is prevented through covalent crosslinking.
In comparative example 1, no imidazolium salt crystal material was prepared by a metal organic framework crystal material, so its electrochemical performance gradually decreased with the operation due to the loss of imidazolium salt without being fixed;
in comparative example 2, no crosslinked structure was formed by using the polyethylene derivative as the framework material of the membrane but the polybenzimidazole as the framework material, the chemical stability was poor, and the performance was deteriorated with the operation.
In comparative example 3, the imidazolium salt crystals were added in a small amount and the ionic transport groups consisted of them were small, so that the conductivity was poor and the mechanical strength was low.
In comparative example 4, the imidazolium salt crystal was added in a large amount, and the conductivity was high, but the brittleness was large and the stretching was easily broken.
Comparative example 5 has a small amount of p-chloromethylstyrene, and the resulting crosslinked structure is incomplete, and has low mechanical strength and low electrical conductivity.
In comparative example 6, the p-chloromethyl styrene is added in a large amount, the prepared film has a crystal structure which is wrapped by the p-chloromethyl styrene, the conductivity is low, and the p-chloromethyl styrene is easy to degrade and has poor stability.
TABLE 1 conductivity and tensile Strength of anion exchange membranes
The anion exchange membranes prepared in the examples of the present invention and the comparative examples were immersed in a 1.0mol/L sodium hydroxide solution for alkali stability test, and the results are shown in Table 2. During the preparation of AEMs, the base stability of AEMs that are not covalently cross-linked is significantly poorer.
Table 2 mass residual rate testing of anion exchange membranes
| Case(s) | Mass residual ratio of 30d exchange membrane% |
| Example 1 | 99.1 |
| Example 2 | 98.7 |
| Example 3 | 98.1 |
| Example 4 | 96.2 |
| Example 5 | 97.2 |
| Comparative example 1 | 91 |
| Comparative example 2 | 78 |
| Comparative example 3 | 89.2 |
| Comparative example 4 | 85 |
| Comparative example 5 | 67.8 |
| Comparative example 6 | 77 |
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A basic anion exchange membrane characterized by: the alkaline anion exchange membrane is compounded by taking an imidazolium salt crystal, polybenzimidazole and polyethylene derivatives as raw materials, wherein the imidazolium salt crystal is as follows: a substance formed by taking 4, 5-disubstituted imidazolium salt as a raw material is fixed in the metal organic framework crystal material; the 4, 5-disubstituted imidazolium salt is 1-butyl C4, C5 disubstituted imidazolium salt or 1-hexyl C4, C5 disubstituted imidazolium salt.
2. The basic anion exchange membrane of claim 1, wherein: the raw material of the imidazolium salt crystal also comprises p-chloromethyl styrene.
3. The basic anion exchange membrane of claim 1, wherein: the metal organic framework crystal material is of a cubic structure with micropores, and the pore diameter of each micropore is 100-1000nm; the metal organic framework crystal material is one or more than two of MIL-101 (Fe), MIL-101 (Cr), MIL-53 (Fe), ZIF-6, ZIF-8 and ZIF-10; the polyethylene derivative is any one of poly-p-chloromethyl styrene and poly-p-chloromethyl-alpha-methyl styrene.
4. The basic anion exchange membrane of claim 2, wherein: the imidazolium salt crystal is synthesized by adopting a low-temperature vacuum method, and comprises the following steps:
(1) Making the metal organic framework crystal material in a vacuum state;
(2) Under the low-temperature environment, mixing the mixed solution of the 4, 5-disubstituted imidazolium salt and the p-chloromethyl styrene with a metal organic framework crystal material, and stirring for reaction;
(3) Centrifuging and drying to obtain the imidazolium salt crystal.
5. The basic anion exchange membrane of claim 4, wherein: the vacuum degree of the vacuum state in the step (1) is-0.6 to-1.0 MPa; the low-temperature reaction temperature in the step (2) is-20 to-10 ℃, the stirring time is 48 to 96 hours, and the molar ratio of the metal organic framework crystal material, the 4, 5-disubstituted imidazolium salt and the chloromethyl styrene is 1; in the step (3), the drying temperature of the precipitate is 60-100 ℃, and the drying time is 4-8h; the steps (1) and (2) are in the same vacuum state.
6. The basic anion exchange membrane of claim 1, wherein: the C4 and C5 substituents in the 1-butyl C4 and C5 disubstituted imidazolium salt or the 1-hexyl C4 and C5 disubstituted imidazolium salt are respectively R 1 And R 2 Said R is 1 And R 2 All of which are methyl, ethyl, propyl, butyl, isopropyl and tert-butyl, and the 1-butyl C4, C5 disubstituted imidazolium salt or 1-hexyl C4, C5 disubstituted imidazolium salt has a structureThe following are respectively:
7. the process for preparing a basic anion exchange membrane according to any of claims 1 to 6, wherein: the method comprises the following steps:
A. preparing a polybenzimidazole high-boiling-point solution, adding a polyethylene derivative at room temperature, and stirring to obtain a mixed solution;
B. adding the imidazolium salt crystal into the mixed solution obtained in the step A, and stirring at room temperature to obtain a membrane casting solution;
C. pouring the membrane casting solution prepared in the step B into a glass mold, and after drying, stripping the obtained membrane from the glass mold;
D. c, soaking the membrane obtained in the step C in an ethanol solution of 4, 5-disubstituted imidazolium salt;
E. and D, soaking the membrane obtained in the step D in alkali liquor, then washing the membrane for more than 5 times by using deionized water, and drying to obtain the alkaline anion exchange membrane.
8. The method of claim 7, wherein:
the preparation method of the polybenzimidazole high-boiling-point solution in the step A comprises the following steps: weighing polybenzimidazole, adding the polybenzimidazole into a high boiling point solvent, and dissolving to obtain a polybenzimidazole high boiling point solution with the mass concentration of 0.5-2wt%, wherein the high boiling point solvent is one of N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide.
9. The method of claim 7, wherein: in the steps A and B, the imidazolium salt crystal is prepared by the following steps in percentage by mass: polybenzimidazole: polyethylene derivative = 1-3.
10. The method of claim 7, wherein: the stirring time of the step A is 24-48h, and the stirring time of the step B is 24-48h; in the step C, drying the casting solution at the temperature of 60-80 ℃ for 24-48h; the mass concentration of the ethanol solution of the 4, 5-disubstituted imidazolium salt in the step D is 1-5wt%, and the soaking time is 24-48h; and E, the alkaline solution in the step E is one of a sodium hydroxide solution or a potassium hydroxide solution, the concentration of the alkaline solution is 0.1-2mol/L, the soaking time is 24-48h, and the drying temperature is 50-60 ℃.
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