CN115948051B - 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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- CN115948051B CN115948051B CN202210861241.XA CN202210861241A CN115948051B CN 115948051 B CN115948051 B CN 115948051B CN 202210861241 A CN202210861241 A CN 202210861241A CN 115948051 B CN115948051 B CN 115948051B
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 96
- 150000004693 imidazolium salts Chemical class 0.000 claims abstract description 77
- 239000012528 membrane Substances 0.000 claims abstract description 46
- -1 polyethylene Polymers 0.000 claims abstract description 37
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 36
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000002791 soaking Methods 0.000 claims abstract description 29
- 238000005266 casting Methods 0.000 claims abstract description 27
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 26
- 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
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 67
- 238000001035 drying Methods 0.000 claims description 44
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 43
- 238000005303 weighing Methods 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 238000002156 mixing Methods 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
- 239000007788 liquid Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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 4
- 150000002500 ions Chemical class 0.000 abstract description 13
- 230000003113 alkalizing effect Effects 0.000 abstract description 11
- 239000000446 fuel Substances 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000003014 ion exchange membrane Substances 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 210000000170 cell membrane Anatomy 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 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
- 239000003513 alkali Substances 0.000 description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 12
- 235000019353 potassium silicate Nutrition 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- RVZHVQZQEPMTQJ-UHFFFAOYSA-N ethanol;1h-imidazole Chemical compound CCO.C1=CNC=N1 RVZHVQZQEPMTQJ-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 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
- 230000006870 function Effects 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal 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
- 238000011160 research Methods 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
- 230000004308 accommodation Effects 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
- 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
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 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
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 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
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 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
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-linked alkaline anion exchange membrane and a preparation method thereof. The alkaline anion exchange membrane is formed by compounding imidazolium salt crystals, polybenzimidazole and polyethylene derivatives as raw materials, wherein the synthesis of the imidazolium salt crystals adopts a low-temperature vacuum method to fix substances formed by taking 4, 5-disubstituted imidazolium salts as raw materials in a metal organic framework crystal material; the alkaline anion exchange membrane is prepared by forming a polymer solution by polybenzimidazole and polyethylene derivatives, adding the polymer solution into imidazolium salt crystals to obtain functionalized casting solution, soaking the prepared exchange membrane in an ethanol solution of 4, 5-disubstituted imidazolium salt, and alkalizing to obtain the high-conductivity crosslinked alkaline anion exchange membrane. 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
In the situation that the current environmental problems are more and more serious, and the energy conservation and emission reduction are under the requisite situation, the development and the utilization of efficient, clean and sustainable energy technology are more and more important. An alkaline Anion Exchange Membrane Fuel Cell (AEMFC) can be used as one of fuel cells and 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 catalyst combines the advantages of proton exchange membrane fuel cells and alkaline fuel cells, adopts solid polymers which are easy to package as electrolytes, greatly improves the activity and stability of the catalyst under alkaline conditions compared with those under acidic conditions, gets rid of the dependence on noble metal catalysts such as platinum and the like, and provides new hopes for large-scale commercial application of the fuel cells.
As a core component of an alkaline membrane fuel cell, development of an alkaline membrane (AEMs) has been an important point and difficulty of research in the field, but the membrane has problems of contradiction between ion exchange capacity and mechanical properties, low ion conductivity, poor chemical stability, and the like. The crosslinked structure can improve the dimensional stability of the membrane, but the conductivity loss is serious. The traditional alkaline membrane mainly adopts polyphenyl ether and polyarylethersulfone polymers as framework materials. At present, the key to the development of AEMFC is the development of alkaline membranes (AEMs), whose ionic conductivity and chemical stability are key parameters, determining the core parameters of fuel cell such as output power, energy density and service life. Compared with Proton Exchange Membranes (PEM), AEMs conduct OH-, and have larger OH-ion radius than H+, and have the defect of low ion conductivity and the like. On the other hand, since alkaline membranes are susceptible to chemical degradation, especially in cases where there is insufficient hydration within the membrane, this is more serious. From the above, it can be seen that the improvement of the ionic conductivity and chemical stability of AEMs is an important issue to be solved.
The synthesis of novel cations to replace quaternary ammonium groups has become a hot point of recent researches, imidazole is taken as a cation functional group, is a five-membered ring with pi conjugated structure, and the resonance effect existing in the ring can weaken the density of electron cloud, so that the attack of OH - is weakened, the stability is improved, but the imidazole is grafted on different main chains, and the distinct alkali stability is shown. At present, the alkali resistance stability of imidazole functional groups is improved to a certain extent mainly through the C2, N1 and N3 substituent group effect.
However Hugar et al found that simple N1, C2 modified imidazoles still had degradation problems, and when the C4, C5 positions on the imidazole ring were substituted with substituents, they were stable in 5M KOH at 80℃for more than 30 days, but current studies on C4, C5 substituted imidazoles AEMs were few, and the AEMs of imidazoles as functional groups exhibited very low conductivity and battery discharge performance, and the mechanism of compatibility of such imidazoles with Pt-based catalysts was still under intense investigation. Therefore, on the premise of ensuring that the imidazole AEMs have high chemical stability, how to increase the number of functional groups and prevent the loss of the functional groups becomes a key problem to be solved.
Disclosure of Invention
The invention aims to provide a high-conductivity crosslinking type alkaline anion exchange membrane and a preparation method thereof, and aims to solve the problems of low conductivity and short service life of the alkaline anion exchange membrane by increasing the number of functional groups and preventing the loss of the functional groups while ensuring high chemical stability.
The technical aim of the invention is realized by the following technical scheme:
The invention provides an alkaline anion exchange membrane, which is formed by compounding imidazolium salt crystals, polybenzimidazole and polyethylene derivatives as raw materials, wherein the imidazolium salt crystals are as follows: fixing a substance formed by taking 4, 5-disubstituted imidazolium salt as a raw material in a 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 scheme, further, the raw material of the imidazolium salt crystal further comprises p-chloromethylstyrene.
In the above technical scheme, further, the metal organic framework crystal material has a cubic structure with micropores, and the aperture 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 scheme, further, the imidazolium salt crystal is synthesized by adopting a low-temperature vacuum method, and the 4, 5-disubstituted imidazolium salt and other raw materials are reacted and fixed in the crystal material of the metal organic framework material with the microporous cube structure, comprising the following steps:
(1) Placing the metal organic frame crystal material into a Schlenk tube provided with a constant pressure funnel, and continuously vacuumizing to enable the metal organic frame crystal material to be in a vacuum state;
(2) Mixing the mixed solution of the 4, 5-disubstituted imidazolium salt and the p-chloromethyl styrene with a metal organic framework crystal material in a low-temperature environment, and stirring to react the 4, 5-disubstituted imidazolium salt with the p-chloromethyl styrene;
(3) After the reaction, the precipitate was dried by centrifugation, and vinyl groups in p-chloromethylstyrene were self-crosslinked to obtain imidazolium salt crystals.
In the technical scheme, further, the vacuum degree of the vacuum state in the step (1) is minus 0.6 to minus 1.0MPa; the low-temperature reaction temperature in the step (2) is-20 to-10 ℃, the stirring time is 48-96 hours, and the molar ratio of the metal organic framework crystal material to the 4, 5-disubstituted imidazolium salt to the p-chloromethyl styrene is 1:2:0.5-5; the drying temperature of the precipitate in the step (3) 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 scheme, further, 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 R 1 and R 2 respectively, and both R 1 and R 2 are any one of methyl, ethyl, propyl, butyl, isopropyl and tert-butyl, and the structures of the 1-butyl C4 and C5 disubstituted imidazolium salt or the 1-hexyl C4 and C5 disubstituted imidazolium salt are 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 the imidazolium salt crystal into the polybenzimidazole/polyethylene derivative mixed solution obtained in the step A, and stirring at room temperature to obtain functionalized casting solution;
C. pouring the casting film liquid prepared in the step B into a glass mold, fully drying, and stripping the obtained film from the glass mold;
D. Soaking the membrane obtained in the step C in an ethanol solution of 4, 5-disubstituted imidazolium salt, and then fishing out;
E. and D, soaking the membrane fished out in the step D in an alkaline solution, then cleaning the membrane with deionized water for more than 5 times, and drying to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
In the above technical scheme, further, the preparation method of the polybenzimidazole high boiling point solution in the step A comprises the following steps: and 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 of the step A is 24-48h, the stirring time of the step B is 24-48h, and the mixing is uniform.
In the above technical solution, further, in steps a and B, the imidazolium salt crystals are calculated according to mass ratio: polybenzimidazole: polyethylene derivative = 1:1-3:1-1.5.
In the technical scheme, the drying temperature of the casting solution in the step C is 60-80 ℃ and the drying time is 24-48 hours; the mass concentration of the ethanol solution of the 4, 5-disubstituted imidazolium salt in the step D is 1 to 5 weight percent, and the soaking time is 24 to 48 hours.
In the technical scheme, 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 of the present invention comprises imidazolium salt crystals, polybenzimidazole and polyethylene derivatives. Firstly, an imidazolium salt crystal takes an 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, and the metal organic framework in the metal organic framework crystal material provides accommodation sites for vinyl compounds in the imidazolium salt and chloromethyl styrene, so that the prepared anion exchange membrane can not cause chemical degradation of an ionic membrane and loss of functional ionic groups due to the change of reaction environment, and on the other hand, the compounds with ion transmission functions such as the imidazolium salt can uniformly and orderly transmit ions due to the highly ordered lattice structure of the metal organic framework crystal material, thereby ensuring continuity and stability of ion transmission, reducing ion transmission resistance, improving ion transmission efficiency and further improving electrochemical performance;
the polybenzimidazole and polyethylene derivatives which do not contain unstable end groups such as ether bonds are taken as the molecular skeleton of the anion exchange membrane, on one hand, the stability in alkaline environment is better, on the other hand, the compatibility between the polymer such as the polybenzimidazole and the polyethylene derivatives and the metal organic framework crystal material is good, and the imidazolium salt crystal prepared by using the metal organic framework crystal material can be uniformly dispersed in the solution formed by the polymer, so that the defects of agglomeration, uneven distribution and the like do not occur; on the other hand, the polybenzimidazole/polyethylene derivative covalent crosslinking effect forms a stable network structure, has strong mechanical strength and corrosion resistance, and can effectively improve the stability of the ion exchange membrane and prevent the ion exchange membrane from being excessively swelled by the combined action of the polybenzimidazole/polyethylene derivative and the metal organic framework in a 'fixed' form so as to achieve the purpose of improving the ion transfer characteristic and chemical stability of the reinforced membrane.
2. As 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 'fixing' with a metal organic framework, namely, after the imidazolium salt reacts with vinyl compounds in chloromethyl styrene, the molecular structure becomes large, the pore diameter in the crystal structure is unchanged, and at the moment, the imidazolium salt can be firmly fixed in the crystal structure of the metal organic framework, so that the loss phenomenon is avoided, namely, the number of functional groups in the membrane is effectively increased; in addition, in the synthesis process of the imidazolium salt crystal, a low-temperature vacuum mode is adopted, and as the 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, deterioration can not occur, and the p-chloromethyl styrene and the imidazolium salt can be smoothly pressed into a crystal structure under the action of negative pressure and then locked, so that the number of functional groups in a film is further ensured;
3. according to the invention, the prepared imidazolium salt crystal is used as an additive, so that the metal organic framework material can fix the functional material, on one hand, the loss of single-component compounds along with the use of the membrane is prevented, and meanwhile, the single component has no ion transmission function, and if the imidazolium salt and the organic framework material are respectively mixed and added, the effect of fixing and stably conducting ions can not be achieved.
4. After the anion exchange membrane is prepared, the anion exchange membrane is soaked and alkalized and functionalized by adopting alkaline solution, so that chloride ions and the like in the imidazolium salt structure are replaced by OH -, the composite membrane is fully alkalized, and the poison of the chloride ions to the catalyst can not be generated in the use process.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
(1) 6.99g (0.01 mol) of MIL-101 (Fe) was weighed into a Schlenk tube equipped with a constant pressure funnel, continuously evacuated to maintain the vacuum degree at-1.0 MPa, and the temperature of the Schlenk tube was lowered 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 fully react the 1-hexyl-4, 5-dimethylimidazolium salt with the p-chloromethylstyrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) Weighing 2g of polybenzimidazole and dissolving in 398g N-methylpyrrolidone at 25 ℃, then weighing 1g of poly-p-chloromethyl styrene and adding, and fully stirring for 24 hours for dissolution;
(5) Weighing 0.67g of imidazolium salt crystal, adding the crystal into the step (4), and continuously maintaining the temperature at 25 ℃ and stirring for 24 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 99g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 1%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 24 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 48 hours at 50 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Example 2:
(1) 7.19g (0.01 mol) of MIL-101 (Cr) was weighed into a Schlenk tube equipped with a constant pressure funnel, continuously evacuated to maintain the vacuum degree at-0.8 MPa, and the temperature of the Schlenk tube was lowered to-15 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-hexyl-4, 5-diethyl imidazolium salt and 1.525g (0.01 mol) of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 36 hours to fully react the 1-hexyl-4, 5-ethylimidazolium salt with the p-chloromethyl styrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying the precipitate at 80 ℃ for 6 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) 2g of polybenzimidazole is weighed and dissolved in 198g of N, N-dimethylformamide at 25 ℃, then 1.2g of poly-p-chloromethyl styrene is weighed and added, and the mixture is fully stirred for 24 hours for dissolution;
(5) Weighing 1g of imidazolium salt crystal, adding the crystal into the step (4), and continuously maintaining the temperature at 25 ℃ and stirring for 36 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 70 ℃ for 36 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 39g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 2.5%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 36h, fishing out, repeatedly washing for 10 times by using deionized water, soaking in 1mol/L sodium hydroxide solution, fully alkalizing for 36h, taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 36 at 55 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Example 3:
(1) Weighing 2.3g (0.01 mol) of ZIF-8, placing in a Schlenk tube provided with a constant pressure funnel, continuously vacuumizing to maintain the vacuum degree at-0.6 MPa, and reducing the temperature of the Schlenk tube to-20 ℃;
(2) Weighing a mixed solution of 3.04 (0.02 mol) of 1-butyl-4, 5-dimethyl imidazolium salt and 1.525g (0.01 mol) of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), and continuously stirring for 48 hours to fully react the 1-butyl-4, 5-dimethyl imidazolium salt with the p-chloromethyl styrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying the precipitate at 100 ℃ for 4 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) Weighing 4g of polybenzimidazole to be dissolved in 196g of N, N-dimethylformamide at 25 ℃, then weighing 4g of poly-p-chloromethyl-alpha-methylstyrene to be added, and fully stirring for 24 hours to be dissolved;
(5) Weighing 4g of imidazolium salt crystals, adding the crystals into the step (4), and continuously maintaining the temperature at 25 ℃ and stirring for 24 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 19g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 5%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 48 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 2mol/L potassium hydroxide solution, fully alkalizing for 48 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 24 hours at 60 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Example 4:
(1) 6.99g (0.01 mol) of MIL-101 (Fe) was weighed into a Schlenk tube equipped with a constant pressure funnel, continuously evacuated to maintain the vacuum degree at-1.0 MPa, and the temperature of the Schlenk tube was lowered to-10 ℃;
(2) Weighing 3.04 (0.02 mol) of 1-hexyl-4, 5-dimethyl imidazolium salt and 0.7625g (0.005 mol) of p-chloromethyl styrene, injecting the mixture into the Schlenk tube in the step (1), and continuously stirring for 96 hours to fully react the 1-hexyl-4, 5-dimethyl imidazolium salt with the p-chloromethyl styrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) Weighing 2g of polybenzimidazole and dissolving in 398g N-methylpyrrolidone at 25 ℃, then weighing 1g of poly-p-chloromethyl styrene and adding, and fully stirring for 24 hours for dissolution;
(5) Weighing 0.67g of imidazolium salt crystal, adding the crystal into the step (4), and continuously maintaining the temperature at 25 ℃ and stirring for 24 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 99g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 1%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 24 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 48 hours at 50 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Example 5:
(1) 6.99g (0.01 mol) of MIL-101 (Fe) was weighed into a Schlenk tube equipped with a constant pressure funnel, continuously evacuated to maintain the vacuum degree at-1.0 MPa, and the temperature of the Schlenk tube was lowered 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 fully react the 1-hexyl-4, 5-dimethylimidazolium salt with the p-chloromethylstyrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) Weighing 2g of polybenzimidazole and dissolving in 398g N-methylpyrrolidone at 25 ℃, then weighing 1g of poly-p-chloromethyl styrene and adding, and fully stirring for 24 hours for dissolution;
(5) Weighing 0.67g of imidazolium salt crystal, adding the crystal into the step (4), and continuously maintaining the temperature at 25 ℃ and stirring for 24 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 99g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 1%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 24 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 48 hours at 50 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Comparative example 1:
(1) Weighing 2g of polybenzimidazole and dissolving in 398g N-methylpyrrolidone at 25 ℃, then weighing 1g of poly-p-chloromethyl styrene and adding, fully stirring and dissolving to obtain casting solution;
(2) Drying the film casting liquid glass die obtained in the step (1) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(3) 1.0g of imidazolium salt is weighed and added into 99g of ethanol to obtain an ethanol solution of the imidazolium salt with the concentration of 1 percent;
(4) Placing the membrane obtained in the step (2) into the solution prepared in the step (3), soaking for 24 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 48 hours at 50 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Comparative example 2:
(1) 6.99g (0.01 mol) of MIL-101 (Fe) was weighed into a Schlenk tube equipped with a constant pressure funnel, continuously evacuated to maintain the vacuum degree at-1.0 MPa, and the temperature of the Schlenk tube was lowered 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 fully react the 1-hexyl-4, 5-dimethylimidazolium salt with the p-chloromethylstyrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) Weighing 2g of polybenzimidazole to be dissolved in 398g N-methylpyrrolidone at 25 ℃, then weighing 0.67g of imidazolium salt crystal to be added into the step (4), and continuously maintaining the temperature of 25 ℃ and stirring for 24 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 99g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 1%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 24 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 48 hours at 50 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Comparative example 3:
(1) 6.99g (0.01 mol) of MIL-101 (Fe) was weighed into a Schlenk tube equipped with a constant pressure funnel, continuously evacuated to maintain the vacuum degree at-1.0 MPa, and the temperature of the Schlenk tube was lowered to-10 ℃;
(2) 1.52 (0.01 mol) of 1-hexyl-4, 5-dimethylimidazolium salt and 1.525g (0.01 mol) of p-chloromethylstyrene were weighed and injected into the Schlenk tube of step (1), and stirring was continued for 96 hours to allow the 1-hexyl-4, 5-dimethylimidazolium salt to react well with the p-chloromethylstyrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) At 25 ℃, 2g of polybenzimidazole is weighed and dissolved in 398g N-methyl pyrrolidone, then 1g of poly-p-chloromethyl styrene is weighed and added, and the mixture is fully stirred and dissolved;
(5) Weighing 0.67g of imidazolium salt crystal, adding the crystal into the step (4), and continuously maintaining the temperature at 25 ℃ and stirring for 24 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 99g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 1%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 24 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 48 hours at 50 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Comparative example 4:
(1) 6.99g (0.01 mol) of MIL-101 (Fe) was weighed into a Schlenk tube equipped with a constant pressure funnel, continuously evacuated to maintain the vacuum degree at-1.0 MPa, and the temperature of the Schlenk tube was lowered 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 96 hours to fully react the 1-hexyl-4, 5-dimethylimidazolium salt with the p-chloromethylstyrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) At 25 ℃, 2g of polybenzimidazole is weighed and dissolved in 398g N-methyl pyrrolidone, then 1g of poly-p-chloromethyl styrene is weighed and added, and the mixture is fully stirred and dissolved;
(5) Weighing 0.67g of imidazolium salt crystal, adding the crystal into the step (4), and continuously maintaining the temperature at 25 ℃ and stirring for 24 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 99g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 1%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 24 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 48 hours at 50 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
Comparative example 5:
(1) 6.99g (0.01 mol) of MIL-101 (Fe) was weighed into a Schlenk tube equipped with a constant pressure funnel, continuously evacuated to maintain the vacuum degree at-1.0 MPa, and the temperature of the Schlenk tube was lowered to-10 ℃;
(2) Weighing 3.04 (0.02 mol) of 1-hexyl-4, 5-dimethyl imidazolium salt and 0.38125g (0.0025 mol) of p-chloromethyl styrene, injecting the mixture into the Schlenk tube in the step (1), and continuously stirring for 96 hours to fully react the 1-hexyl-4, 5-dimethyl imidazolium salt with the p-chloromethyl styrene;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable vinyl to be self-crosslinked to form imidazolium salt crystals;
(4) At 25 ℃, 2g of polybenzimidazole is weighed and dissolved in 398g N-methyl pyrrolidone, then 1g of poly-p-chloromethyl styrene is weighed and added, and the mixture is fully stirred and dissolved;
(5) Weighing 0.67g of imidazolium salt crystal, adding the crystal into the step (4), and continuously maintaining the temperature at 25 ℃ and stirring for 24 hours to obtain casting solution;
(6) Drying the film casting liquid glass die obtained in the step (5) at 60 ℃ for 48 hours, and stripping the dried film from the glass plate for later use;
(7) Weighing 1.0g of the imidazolium salt crystals prepared in the step (3), and adding the crystals into 99g of ethanol to obtain an imidazolium salt ethanol solution with the concentration of 1%;
(8) Placing the membrane obtained in the step (6) into the solution prepared in the step (7), soaking for 24 hours, fishing out, repeatedly washing for 10 times by using deionized water, then soaking in 0.1mol/L sodium hydroxide solution, fully alkalizing for 24 hours, then taking out the alkali solution washed off the surface of the membrane by using the deionized water, and thoroughly drying for 48 hours at 50 ℃ to obtain the high-conductivity crosslinked alkaline anion exchange membrane.
In comparative examples 1 to 5, no imidazolium salt crystals were added in comparative example 1, no polyethylene derivative was added in comparative example 2, and in comparative examples 3 to 6, too much or too little imidazolium salt and p-chloromethylstyrene were added, respectively. The basic anion exchange membranes of the examples and the comparative examples were subjected to the conductivity and tensile strength tests, and the results are shown in table 1. As can be seen from Table 1, the prepared exchange membrane of the present invention has higher conductivity and tensile strength, and the effect is better than that of the comparative example. The imidazolium salt is introduced into AEMs in two forms of covalent cross-linking and metal organic framework 'fixing', so that the number of functional groups in a membrane is increased, a regular ordered ion transfer channel is constructed by means of a regular lattice structure, and ion transfer resistance is reduced; meanwhile, polybenzimidazole/polyvinyl benzyl chloride is adopted as a molecular framework, and the stability of the ion exchange membrane is improved and the ion exchange membrane is prevented from being excessively swelled through covalent crosslinking.
The comparative example 1 does not produce an imidazolium salt crystal material by a metal-organic framework crystal material, so its electrochemical performance gradually decreases with the operation, because the imidazolium salt is not immobilized and runs off;
In comparative example 2, a polyethylene derivative was not used as a backbone material of the film, but polybenzimidazole was used as the backbone material, a crosslinked structure was not formed, and the chemical stability was poor and the performance was deteriorated with running.
The imidazolium salt crystals of comparative example 3 were added in a small amount and had a small amount of ion-transporting groups, so that the electric conductivity was poor and the mechanical strength was also low.
The imidazolium salt crystals of comparative example 4 were added in a large amount and had high conductivity, but were brittle and easy to crack in stretching.
In comparative example 5, the addition amount of p-chloromethyl styrene was small, and the crosslinked structure formed was incomplete, and the mechanical strength and conductivity were low.
In comparative example 6, the amount of p-chloromethyl styrene added is large, the prepared film crystal structure is wrapped inside, the conductivity is low, and meanwhile, 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 and comparative examples of the present invention were immersed in 1.0mol/L sodium hydroxide solution for alkali stability test, and the results are shown in Table 2. The alkali stability of the AEMs without covalent cross-linking is markedly poorer during the preparation of the AEMs.
TABLE 2 Mass residual Rate testing of anion exchange membranes
| Case (B) | Mass residual rate/%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 explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.
Claims (9)
1. A basic anion exchange membrane characterized by: the alkaline anion exchange membrane is formed by compounding imidazolium salt crystals, polybenzimidazole and polyethylene derivatives as raw materials, wherein the imidazolium salt crystals are as follows: fixing a substance formed by taking 4, 5-disubstituted imidazolium salt as a raw material in a 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;
the raw materials of the imidazolium salt crystal also comprise p-chloromethylstyrene;
The molar ratio of the 4, 5-disubstituted imidazolium salt, the metal organic framework crystal material and the p-chloromethyl styrene is 2:1:0.5-5.
2. The basic anion exchange membrane of claim 1, wherein: the metal organic framework crystal material is of a cubic structure with micropores, and the aperture 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.
3. The basic anion exchange membrane of claim 1, wherein: the imidazolium salt crystal is synthesized by adopting a low-temperature vacuum method, and comprises the following steps:
(1) The metal organic framework crystal material is in a vacuum state;
(2) Mixing the mixed solution of the 4, 5-disubstituted imidazolium salt and the p-chloromethyl styrene with a metal organic framework crystal material in a low-temperature environment, and stirring for reaction;
(3) Centrifuging and drying to obtain imidazolium salt crystals.
4. A basic anion exchange membrane according to claim 3, characterized in that: the vacuum degree of the vacuum state in the step (1) is minus 0.6 to minus 1.0MPa; the low-temperature reaction temperature in the step (2) is-20 to-10 ℃, the stirring time is 48-96h, the precipitate drying temperature in the step (3) is 60-100 ℃, and the drying time is 4-8h; the steps (1) and (2) are in the same vacuum state.
5. 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 R 1 and R 2 respectively, the R 1 and R 2 are any one of methyl, ethyl, propyl, butyl, isopropyl and tert-butyl, and the structures of the 1-butyl C4 and C5 disubstituted imidazolium salt or the 1-hexyl C4 and C5 disubstituted imidazolium salt are as follows:
1-butyl C4, C5 disubstituted imidazolium salt 1-hexyl C4, C5 disubstituted imidazolium salt.
6. A process for preparing a basic anion exchange membrane as claimed in any one of claims 1 to 5, characterized in that: 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 in the step A, and stirring at room temperature to obtain a casting solution;
C. Pouring the casting film liquid prepared in the step B into a glass mold, drying, and stripping the obtained film from the glass mold;
D. soaking the membrane obtained in the step C in an ethanol solution of 4, 5-disubstituted imidazolium salt;
E. and D, soaking the membrane in alkaline liquor, then washing the membrane with deionized water for more than 5 times, and drying to obtain the alkaline anion exchange membrane.
7. The method of manufacturing according to claim 6, wherein:
The preparation method of the polybenzimidazole high-boiling-point solution in the step A comprises the following steps: and 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.
8. The method of manufacturing according to claim 6, wherein: in the steps A and B, the mass ratio of the imidazolium salt crystals is as follows: polybenzimidazole: polyethylene derivative = 1:1-3:1-1.5.
9. The method of manufacturing according to claim 6, wherein: the stirring time of the step A is 24-48h, and the stirring time of the step B is 24-48h; the drying temperature of the casting solution in the step C 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 to 5 weight percent, and the soaking time is 24 to 48 hours; the alkaline solution in the step E is one of sodium hydroxide solution or 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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| CN115948051A (en) | 2023-04-11 |
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