CN114854063A - Piperidine anion exchange membrane with excellent comprehensive performance and preparation method thereof - Google Patents
Piperidine anion exchange membrane with excellent comprehensive performance and preparation method thereof Download PDFInfo
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- CN114854063A CN114854063A CN202210635637.2A CN202210635637A CN114854063A CN 114854063 A CN114854063 A CN 114854063A CN 202210635637 A CN202210635637 A CN 202210635637A CN 114854063 A CN114854063 A CN 114854063A
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- CDZAAIHWZYWBSS-UHFFFAOYSA-N 2-bromoethyl prop-2-enoate Chemical compound BrCCOC(=O)C=C CDZAAIHWZYWBSS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 18
- -1 styrene compound Chemical class 0.000 claims abstract description 18
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical group [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 150000002500 ions Chemical class 0.000 abstract description 13
- 230000005540 biological transmission Effects 0.000 abstract description 10
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 35
- 230000008961 swelling Effects 0.000 description 17
- 239000000446 fuel Substances 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- QFDISQIDKZUABE-UHFFFAOYSA-N 1,1'-bipiperidine Chemical compound C1CCCCN1N1CCCCC1 QFDISQIDKZUABE-UHFFFAOYSA-N 0.000 description 4
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001002 functional polymer Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 102000004310 Ion Channels Human genes 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XIXNSLABECPEMI-VURMDHGXSA-N (z)-2-[2-[(2-methylpropan-2-yl)oxycarbonylamino]-1,3-thiazol-4-yl]pent-2-enoic acid Chemical compound CC\C=C(/C(O)=O)C1=CSC(NC(=O)OC(C)(C)C)=N1 XIXNSLABECPEMI-VURMDHGXSA-N 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012698 light-induced step-growth polymerization Methods 0.000 description 1
- VXYRWKSIAWIQMG-UHFFFAOYSA-K manganese(2+) N-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate triphenylstannyl acetate Chemical compound [Mn++].[S-]C(=S)NCCNC([S-])=S.CC(=O)O[Sn](c1ccccc1)(c1ccccc1)c1ccccc1 VXYRWKSIAWIQMG-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
A piperidine anion exchange membrane with excellent comprehensive performance and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving 2-bromoethyl acrylate in an organic solvent, adding 2- (butyltrithiocarbonate) propionic acid and a photocatalyst, and carrying out photopolymerization reaction under an argon atmosphere to obtain a first reaction solution; adding a styrene compound, an organic solvent and a photocatalyst into the first reaction solution, and carrying out photopolymerization reaction under an argon atmosphere to obtain a second reaction solution; precipitating the second reaction solution in ethanol, and purifying for multiple times to obtain a block polymer; dissolving the block polymer in an organic solvent, adding N-methylpiperidine, and performing piperidine functionalization reaction in an oil bath to obtain a third reaction liquid; and coating the third reaction solution on a substrate, and drying to obtain the piperidine anion-exchange membrane. The piperidine anion exchange membrane of the invention obtains higher ion transmission efficiency under the condition of lower ion exchange capacity, and realizes high ion conductivity under the condition of low water content.
Description
Technical Field
The invention relates to the field of fuel cell membrane materials, in particular to a piperidine anion exchange membrane with excellent comprehensive performance and a preparation method thereof.
Background
Anion exchange membrane fuel cells are of interest because of their ability to combine the advantages of proton exchange membrane fuel cells with conventional alkaline fuel cells. Anion exchange membrane fuel cells can also potentially address many of the disadvantages of proton exchange membrane fuel cells, such as catalyst cost, reduction reaction kinetics, and fuel permeation. The performance of an anion exchange membrane, which is one of the key components of an anion exchange membrane fuel cell, directly affects the service life and the final performance of the cell. The mutual restriction effect between ionic conductivity and water swelling and chemical stability are two main properties of anion exchange membranes.
In order to prepare an anion exchange membrane with the mutual restriction effect between the ionic conductivity and the water swelling and the lasting chemical stability, researchers design a main chain type negative membrane, a side chain type negative membrane, a block type negative membrane and the like. The main chain type negative membrane is connected on the main chain directly or by short chain intervals due to ionic functional groups, and the negative membrane with the configuration is generally low in ionic conductivity, high in water swelling rate and poor in alkali resistance. Compared with the main chain type negative membrane, the side chain type negative membrane can more effectively construct an ion channel, so that the ion conductivity and alkali resistance of the membrane can be improved to a certain extent, but the effect is not ideal. Compared with anion exchange membranes with other configurations, the block type anion exchange membrane has the advantage that high ion conductivity is easier to obtain, and the block type anion exchange membrane is mainly characterized in that the block polymer can form an oriented and continuous through hydrophilic/hydrophobic channel, so that a channel is provided for ion transmission, and the ion transmission performance is improved. However, the prior art "block-type negative film" cannot ensure a complete vacuum and argon atmosphere during the synthesis of the block precursor, so that the repeatability is poor, and the mutual restriction effect between the ionic conductivity and the water swelling is not well reflected, specifically, the conductivity is very low (the Cl-type conductivity is 5.94mS/cm at 30 ℃ and 9.84mS/cm at 60 ℃) when the water swelling is very low, so that the application is limited, and the practical use requirement of the fuel cell cannot be met.
Disclosure of Invention
Based on the above, the invention provides a piperidine anion exchange membrane with excellent comprehensive performance and a preparation method thereof, so as to solve the technical problem that the block type anion exchange membrane for a fuel cell in the prior art has low conductivity under the condition of low water swelling.
In order to achieve the above object, the present invention provides a method for preparing a piperidine anion-exchange membrane with excellent overall performance, comprising the steps of:
1) dissolving 2-bromoethyl acrylate in an organic solvent, adding 2- (butyltrithiocarbonate) propionic acid and a photocatalyst, and carrying out photopolymerization reaction by adopting visible light under an argon atmosphere to obtain a first reaction solution;
2) adding a styrene compound, an organic solvent and a photocatalyst into the first reaction solution obtained in the step 1), and carrying out photopolymerization reaction by adopting visible light under an argon atmosphere to obtain a second reaction solution;
3) precipitating the second reaction solution obtained in the step 2) in ethanol, and purifying for multiple times to obtain a block polymer;
4) dissolving the block polymer obtained in the step 3 in an organic solvent, adding N-methylpiperidine, and performing piperidine functionalization reaction in an oil bath to obtain a third reaction solution;
5) coating the third reaction solution obtained in the step 4) on a substrate, and drying to obtain the piperidine anion-exchange membrane.
As a further preferred embodiment of the present invention, the photopolymerization reactions carried out in steps 1 and 2) are carried out in a closed reaction vessel, and after all the corresponding reactants are added and before the photopolymerization reaction, the reaction vessel is subjected to freezing, vacuum pumping, thawing, and argon gas introduction treatment, and the cycle is repeated for a plurality of times.
As a further preferred embodiment of the present invention, the time for carrying out the photopolymerization reaction in the steps 1 and 2) is 0.5 to 1 hour and 12 to 24 hours, respectively.
In a further preferred embodiment of the present invention, the photocatalyst is tris (phenylpyridine) iridium complex, and both steps 1 and 2) are photopolymerized by blue light irradiation.
In a further preferred embodiment of the present invention, the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide.
In a more preferred embodiment of the present invention, the styrene-based compound is styrene or a styrene-based compound having a functional group.
In a further preferred embodiment of the present invention, the functional group in the styrene compound is a fluorine-containing functional group.
As a further preferable technical scheme of the invention, the temperature for carrying out the piperidine functionalization reaction in the step 4) is 50-60 ℃ and the time is 12-24 h.
In a more preferred embodiment of the present invention, the molar ratio of the 2-bromoethyl acrylate to the styrene compound is 1:1, and the ratio of the bromine atom in the 2-bromoethyl acrylate to the N-methylpiperidine is N Br :n Pip =1:1.2-1:1.6。
According to another aspect of the invention, the invention also provides a piperidine anion-exchange membrane with excellent comprehensive performance, which is prepared by adopting the preparation method of the piperidine anion-exchange membrane with excellent comprehensive performance.
The piperidine anion exchange membrane with excellent comprehensive performance and the preparation method thereof adopt the technical scheme, and can achieve the following beneficial effects:
1) according to the preparation method, the block polymer with a soft-hard segment structure is synthesized by adopting visible light initiation polymerization, and the piperidine group is introduced into the block polymer to prepare the piperidine anion exchange membrane, because the soft segment and the hard segment are in an ordered structure, clear hydrophilic and hydrophobic micro-phase separation morphology is easily formed, so that effective transmission of anions is promoted, higher ion transmission efficiency can be obtained under the condition of lower ion exchange capacity, and high ion conductivity under the condition of low water content is realized;
2) the piperidine salt introduced in the preparation method has higher alkali resistance stability, so that the prepared piperidine anion-exchange membrane has higher comprehensive performance and has potential application value in an alkaline fuel cell.
3) The preparation method disclosed by the invention is used for carrying out photopolymerization in an argon atmosphere, so that complete vacuum and argon atmosphere in a reaction tube container are ensured, the repeatability is better, and the preparation yield and the comprehensive performance of the piperidine anion exchange membrane are improved.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a NMR spectrum of poly-2-bromoethyl acrylate (PBrEMA) in example 1 of the present invention;
FIG. 2 is a gel permeation chromatogram of poly 2-bromoethyl acrylate (PBrEMA) in example 1 of the present invention;
FIG. 3 is a NMR spectrum of poly (2-bromoethylacrylate-block-polypentafluorostyrene) (PBrEMA-b-PPFSt) in example 1 of the present invention;
FIG. 4 is a gel permeation chromatogram of poly 2-bromoethylacrylate-block-polypentafluorostyrene (PBrEMA-b-PPFSt) in example 1 of the present invention;
FIG. 5 is a hydrogen nuclear magnetic resonance spectrum of a piperidine type anionic polymer (PPiEMA-b-PPFSt) in example 1 of the present invention;
FIG. 6 is a transmission electron microscope of a piperidine anion exchange membrane (PPiEMA-b-PPFSt-x) in examples 1 and 2 of the present invention (where x represents two different IEC, 0.63mmol/g, 1.32mmol/g controlled by the degree of functionalization);
FIG. 7 is a graph showing the water content and swelling ratio of a piperidine anion-exchange membrane (PPiEMA-b-PPFSt-x) according to the temperature in examples 1 and 2 of the present invention;
FIG. 8 is a TG-DTG curve for a piperidine anion exchange membrane (PPiEMA-b-PPFSt-x) according to examples 1 and 2 of the present invention;
FIG. 9 shows the chloride conductivity at different temperatures for the piperidine anion exchange membrane (PPiEMA-b-PPFSt-x) according to the present invention in examples 1 and 2;
FIG. 10 is a graph showing the IEC dependence of time in the piperidine anion exchange membrane (PPiEMA-b-PPFSt-x) soaked in 1M NaOH at 60 ℃ in examples 1 and 2 of the present invention.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
The preparation method of the piperidine anion-exchange membrane with excellent comprehensive performance, provided by the invention, comprises the following steps:
step 1), dissolving 2-bromoethyl acrylate in an organic solvent in a closed reaction container, adding 2- (butyltrithiocarbonate) propionic acid and a photocatalyst, performing repeated freezing-vacuumizing-unfreezing-argon introducing treatment, and performing first-stage photopolymerization by adopting blue light irradiation under an argon atmosphere for 0.5-1h to obtain a first reaction solution;
step 2), adding a styrene compound, an organic solvent and a photocatalyst into the first reaction solution obtained in the step 1) in a closed reaction container, repeatedly freezing, vacuumizing, unfreezing and introducing argon for multiple times, and then performing second photopolymerization for 12-24 hours by using visible light under the argon atmosphere to obtain a second reaction solution;
step 3), adding an organic solvent into the second reaction solution obtained in the step 2) for dilution, then dropwise adding the diluted solution into ethanol for precipitation, and obtaining a pure block polymer after multiple purification;
step 4), dissolving the block polymer obtained in the step 3 in an organic solvent, adding N-methylpiperidine, and performing piperidine functionalization reaction in an oil bath kettle at the temperature of 50-60 ℃ for 12-24 hours to obtain a third reaction solution;
and 5) coating the third reaction solution obtained in the step 4) on a substrate, and drying to obtain the piperidine anion exchange membrane (hereinafter referred to as membrane).
In the preparation method, 2-bromoethyl acrylate is taken as a monomer and 2- (butyl trithiocarbonate) propionic acid is taken as a chain transfer reagent to carry out a photopolymerization reaction to synthesize a flexible chain segment; and then, taking the first reaction solution as a chain transfer reagent and a styrene compound as a monomer, continuously carrying out photopolymerization reaction to synthesize a rigid chain segment, so that the block polymer has a flexible chain segment and a rigid chain, and further the final product membrane has a special soft-hard structure, wherein the structure shows that regular hydrophilic-hydrophobic phase separation is easy to form in the membrane forming process, hydrophilic areas are communicated with each other to form a communicated hydrophilic channel, the smooth and unimpeded channel is provided for ion transmission, the ion transmission efficiency is favorably improved, and the hydrophobic areas ensure the mechanical stability of the membrane. Through piperidine functionalization reaction, a piperidine group is introduced into the block polymer, so that the alkali resistance stability of the membrane is improved, and the membrane can simultaneously have the mutual restriction effect between high conductivity and water swelling and high alkali resistance stability.
The two monomers synthesized by the block polymer are respectively 2-bromoethyl acrylate and a styrene compound, and the photopolymerization activity of the 2-bromoethyl acrylate is higher than that of the styrene compound, so that the first reaction solution can be used as a chain transfer reagent to initiate the continuous photopolymerization of the styrene compound to form the block polymer with a flexible chain segment and a rigid chain, and the piperidine anion-exchange membrane with the flexible chain segment and the rigid chain is obtained.
Specifically, the piperidine anion-exchange membrane has a block structure formed by combining a flexible chain segment and a rigid chain segment, so that the membrane has excellent microphase separation performance, wherein the flexible chain is a polyacrylate segment, and the rigid chain is a polystyrene segment or a monofluoro substituted or polyfluoro polystyrene segment.
In practical application, the molar ratio of the 2-bromoethyl acrylate to the styrene compound is 1:1. Experimental research shows that if the ratio of the two is too high (more than 1: 1), the film is too hard after coating and film forming, and the film is broken when being collided; if the ratio of the two is too low (less than 1 to 1) (i.e. 2-bromoethyl acrylate), the film becomes too soft after coating, and thus, it does not make sense to perform the piperidine functionalization treatment.
In specific implementation, the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide. The styrene compound is styrene or a styrene compound containing functional groups. Among them, the functional group in the styrene-based compound is preferably a group capable of promoting microphase separation of the block polymer, and studies have shown that fluorine atoms improve the performance of the fuel cell membrane and improve the chemical stability and water swelling resistance of the membrane, and therefore, the styrene-based compound is preferably a functional group containing a fluorine element. Further, the styrene compound is preferably pentafluorostyrene.
The invention adopts the photocatalysis method to synthesize the piperidine anion-exchange membrane, the synthesis process can be carried out at room temperature, heating or freezing is not needed during photopolymerization, the operation is simple and convenient, the usage amount of the photocatalyst is less, the ppm level photocatalyst can efficiently catalyze the polymerization reaction, the metal residue is less, and the invention is more environment-friendly.
The light-induced polymerization belongs to free radical polymerization, if the oxygen is not completely removed, the free radical polymerization is unfavorable, and the conversion rate is not high, namely, the photopolymerization reaction is carried out in an argon atmosphere, so that the influence of impurity gas (oxygen) on the polymerization reaction is avoided. Preferably, in steps 1) and 2, after all the corresponding reactants are added into the closed reaction vessel and before photopolymerization, the reaction vessel needs to be subjected to freezing, vacuumizing, thawing and argon introducing treatment, and the cycle is repeated for multiple times, so that the vacuum degree and the argon atmosphere can be improved, and the influence of impurity gas (oxygen) on the polymerization reaction can be further reduced.
Further preferably, the first reaction solution obtained by the polymerization reaction in the step 1) is directly applied to the step 2) as a chain reaction reagent, so that the preparation steps are optimized, raw materials are saved, the operation process is simplified, and the large-scale production is facilitated.
In order to make those skilled in the art further understand the technical solution of the present invention, the technical solution of the present invention is further described in detail by way of examples below.
Example 1
The preparation method of the piperidine anion-exchange membrane with excellent comprehensive performance provided by the embodiment comprises the following specific steps:
1.1 Synthesis of the first reaction solution
5mg (0.02mmol) of the chain transfer reagent 2- (butyltrithiocarbonate) propionic acid (BTPA) was weighed into a 25mL Xinville reaction tube, and 0.5mL (4.1mmol) of 2-bromoethyl acrylate (BrEMA) and 0.010mL (1.34g/mL, 2X 10) were accurately weighed using a pipette -5 ) The photocatalyst tris (phenylpyridine) iridium complex (Ir (ppy) 3 ) 0.5mL of dimethyl sulfoxide (DMSO) is put in the Xinweier reaction tube, and the process of freezing, vacuumizing, unfreezing and introducing argon is carried out for three times to remove the air in the reaction tube, and then the first-stage photopolymerization is carried out by keeping the argon atmosphere; placing the Xinweier reaction tube under a blue light LED lamp at room temperature to irradiate for 1h, wherein the power is 36Watts, and the maximum incident wavelength lambda is max At 456nm, a first reaction solution was obtained.
The first reaction solution contains poly 2-bromoethyl acrylate (PBrEMA) synthesized by the first-stage photopolymerization and having a flexible segment, and the nuclear magnetic resonance hydrogen spectrum and the gel permeation chromatography of the first reaction solution are respectively shown in FIG. 1 and FIG. 2. The chemical formula of the first stage photopolymerization is as shown in formula (1):
1.2 Synthesis of Block Polymer
0.6mL (4.1mmol) of pentafluorostyrene (PFSt), 12. mu.L (1.34g/mL, 2X 10) were measured accurately with a pipette -5 ) The photocatalyst tris (phenylpyridine) iridium complex (Ir (ppy) 3 ) 0.6mL of dimethyl sulfoxide (DMSO) is put in a Xinweier reaction tube and is treated by the processes of freezing, vacuumizing, unfreezing and introducing argon, the process is circulated for three times to remove the air in the reaction tube, and then the argon atmosphere is kept for carrying out second-stage photopolymerization; placing the Xinweier reaction tube under a blue light LED lamp at room temperature for irradiating for 140min, wherein the power is 36Watts, and the maximum incident wavelength lambda is max At 456nm, a second reaction solution was obtained.
The second reaction solution contains poly 2-bromoethyl acrylate-block-polypentafluorostyrene (PBrEMA-b-PPFSt) synthesized by second-stage photopolymerization, and has a flexible chain segment and a rigid chain segment, wherein the nuclear magnetic resonance hydrogen spectrum of the second reaction solution is shown in figure 3, and the gel permeation chromatography of the second reaction solution is shown in figure 4. The chemical formula of the second stage photopolymerization is as shown in formula (2):
and (3) supplementing dimethyl sulfoxide (DMSO) into the second reaction solution for dilution treatment, then dropwise adding the second reaction solution into ethanol for precipitation, and repeatedly purifying for 3 times to obtain a pure block polymer.
1.3 functionalization of Block polymers
0.1g of the block polymer was dissolved in 1mL of dimethyl sulfoxide (DMSO) to form a uniform solution, and then 23. mu.L (n) was added to the solution Br :n Pip 1:1.2) was placed in an oil bath at 60 ℃ for 24 hours to obtain a third reaction solution.
The third reaction solution contains a functionalized polymer (PPiEMA-b-PPFSt) obtained by a piperidine functionalization reaction, which is also called piperidine type anionic polymer, and its nuclear magnetic resonance hydrogen spectrum is shown in fig. 5. The chemical formula of the piperidine functionalization reaction is shown as formula (3):
1.4 Forming of piperidine type anion exchange membranes
And (3) coating the third reaction solution on a clean and tidy glass plate, and drying at 60 ℃ to obtain the piperidine anion exchange membrane (PPiEMA-b-PPFSt-x, wherein x represents an IEC value).
By Mohr's titration, the piperidine type anion exchange membrane prepared in example 1 was found to have an IEC of 0.63 mmol/g.
Example 2
The preparation method and performance test of the piperidine anion-exchange membrane in this example are the same as those in example 1, except that the ratio N of bromine atoms in 2-bromoethyl acrylate to N-methylpiperidine in this example is different from Br :n Pip 1:1.6, so that the degree of functionalization of the piperidine functionalization reactions of the two examples differs, which finally yields a piperidine-type anion-exchange membrane with an IEC of 1.32 mmol/g.
The following performance tests were performed for examples 1 and 2, respectively:
microphase separation morphology characterization was performed on the bipiperidine anion exchange membranes with IEC 0.63mmol/g and 1.32mmol/g by Transmission Electron Microscopy (TEM), respectively, and the results are shown in fig. 6. As can be clearly seen from FIG. 6, the piperidine anion-exchange membrane prepared by the invention has a clear hydrophilic-hydrophobic microphase separation morphology, the hydrophilic regions are mutually communicated to form a through hydrophilic channel, and a smooth channel is provided for the transmission of ions, so that the ion transmission efficiency is improved, the conductivity of the anion-exchange membrane is further improved, and the hydrophobic regions provide mechanical support for the anion-exchange membrane, so that the mechanical stability of the membrane is ensured.
The piperidine anion-exchange membrane with excellent comprehensive performance has such clear hydrophilic-hydrophobic microphase separation appearance mainly because: the prepared functional polymer has a special structure, on one hand, one section of the functional polymer contains a hydrophilic piperidine salt ion functional group, the other section of the functional polymer is hydrophobic by pentafluorostyrene, on the other hand, the functional polymer also has a soft-hard section structure, a first section of polymer in the soft-hard section structure is a flexible chain segment, a second section of polymer is a rigid chain segment, the soft-hard section structure is beneficial to microphase separation, a through ion channel is formed, and the soft-hard section structure is also beneficial to keeping certain mechanical strength of a membrane.
The two piperidine anion exchange membranes with IEC of 0.63mmol/g and 1.32mmol/g were respectively soaked in a glass bottle filled with water at a certain temperature for 24h, and the water content and the linear swelling rate of the membranes were measured, as shown in FIG. 7, the water content of the membrane PPiEMA-b-PPFSt-0.63 at 30 ℃ was 10.81 wt%, the linear swelling rate was 5.93%, the temperature was raised to 80 ℃, the water content and the linear swelling rate were respectively 30.06 wt% and 13.38%, the water content of the membrane PPiEMA-b-PPFSt-1.32 at 30 ℃ was 11.84 wt%, the linear swelling rate was 6.32%, the temperature was raised to 80 ℃, the water content and the linear swelling rate were respectively 33.70 wt% and 16.95%. As can be seen from the figure, the water content and the linear swelling ratio of the piperidine type anion-exchange membrane increase with the increase of the temperature, but the water content value of the high IEC at 80 ℃ is lower than 35 wt%, and the piperidine type anion-exchange membrane can ensure the integrity of the fuel cell running at high temperature.
The heat resistance stability test was performed on each of the bipiperidine type anion exchange membranes having IEC of 0.63mmol/g and 1.32mmol/g, and the thermal decomposition curves of the membranes were obtained, and the test data of the two membranes were the same, as shown in fig. 8, in which the abscissa Temperature represents the Temperature and the ordinate Weight retention rate represents the Weight retention rate of the membrane and the unit is%. As can be seen from the figure, the membrane starts to be thermally decomposed at 168 ℃, the working temperature of a general fuel cell is 60-90 ℃, and the thermal decomposition temperature of the piperidine type anion-exchange membrane is far higher than the use temperature of the membrane, so that the piperidine type anion-exchange membrane prepared by the invention has higher heat-resistant stability.
Cl at different temperatures for IEC 0.63mmol/g and 1.32mmol/g bipiperidine anion-exchange membranes - Type conductivity the measurement was made as shown in FIG. 9, where the chlorine type conductivity of the membrane PPiEMA-b-PPFSt-0.63 was 11.07mS/cm at 30 ℃ and increased to 57.32mS/cm as the temperature increased to 80 ℃. The membrane PPiEMA-b-PPFSt-1.32 has a chlorine type conductivity of 19.75mS/cm at 30 ℃ and increases to 170.55mS/cm with increasing temperature to 80 ℃. It can be seen that the conductivity of the film increases with increasing temperature, which is caused by the mobility of the anions increasing with temperature. The electric conductivity of the membrane PPiEMA-b-PPFSt-1.32 has more obvious trend along with the temperature increase, which is similar to that of the membraneThe phase separation morphology of (2) is corresponding, namely the IEC is larger, the formed ion channel is larger, and the ion transportation is facilitated.
The bipiperidine type anion exchange membrane having IEC of 0.63mmol/g and 1.32mmol/g was immersed in a 1M aqueous NaOH solution at 80 ℃ for 10 days, taken out every two days, and measured for IEC with deionized water, and as a result, as shown in fig. 10, IEC decreased by about 34.9% in 10 days. This shows that the piperidine anion-exchange membrane prepared by the invention has better alkali-resistant stability.
Preferably, the present invention is practiced by altering N-methylpiperidine (N) Br :n Pip 1:1.2-1:16) to achieve a change in the degree of functionalization, if n Br :n Pip Less than 1:1.2, the functionalization degree is too low, so that IEC is too low, and the conductivity is too low; if it is n Br :n Pip Higher than 1:1.6, the degree of functionalization is so high that the polymer crosslinks during functionalization to affect the solubility and IEC of the membrane too high, thereby affecting the interactive effect between the ionic conductivity and water swelling of the membrane.
The best experimental protocol for the present invention is example 2, i.e. n Br :n Pip 1: at 1.6, the linear swelling ratio of the membrane PPiEMA-b-PPFSt-1.32 to the membrane PPiEMA-b-PPFSt-0.63 is not obvious along with the temperature increase, and the conductivity is obviously increased.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (10)
1. A preparation method of a piperidine anion exchange membrane with excellent comprehensive performance is characterized by comprising the following steps:
1) dissolving 2-bromoethyl acrylate in an organic solvent, adding 2- (butyltrithiocarbonate) propionic acid and a photocatalyst, and carrying out photopolymerization reaction by adopting visible light under an argon atmosphere to obtain a first reaction solution;
2) adding a styrene compound, an organic solvent and a photocatalyst into the first reaction solution obtained in the step 1), and carrying out photopolymerization reaction by adopting visible light under an argon atmosphere to obtain a second reaction solution;
3) precipitating the second reaction solution obtained in the step 2) in ethanol, and purifying for multiple times to obtain a block polymer;
4) dissolving the block polymer obtained in the step 3 in an organic solvent, adding N-methylpiperidine, and performing piperidine functionalization reaction in an oil bath to obtain a third reaction solution;
5) coating the third reaction solution obtained in the step 4) on a substrate, and drying to obtain the piperidine anion-exchange membrane.
2. The method for preparing piperidine anion-exchange membrane with excellent overall performance according to claim 1, wherein the photopolymerization reactions performed in steps 1 and 2) are performed in a closed reaction vessel, and after all the corresponding reactants are added and before the photopolymerization reaction, the reaction vessel is subjected to freezing-vacuumizing-unfreezing-argon introducing treatment and is circulated for multiple times.
3. The method for preparing piperidine anion-exchange membrane with excellent overall performance according to claim 1, wherein the time for photopolymerization in steps 1 and 2) is 0.5-1h and 12-24h, respectively.
4. The method for preparing the piperidine anion-exchange membrane with excellent comprehensive performance according to claim 1, wherein the photocatalyst is a tris (phenylpyridine) iridium complex, and steps 1 and 2) are both photopolymerized by blue light irradiation.
5. The method for preparing the piperidine type anion-exchange membrane with excellent comprehensive performance according to claim 1, wherein the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide.
6. The method for preparing the piperidine anion-exchange membrane with excellent comprehensive performance according to claim 1, wherein the styrene compound is styrene or a styrene compound containing functional groups.
7. The method for preparing the piperidine anion-exchange membrane with excellent comprehensive performance according to claim 6, wherein the functional group in the styrene compound is a fluorine-containing functional group.
8. The method for preparing the piperidine anion-exchange membrane with excellent comprehensive performance according to claim 1, wherein the temperature for performing the piperidine functionalization reaction in the step 4) is 50-60 ℃ and the time is 12-24 h.
9. The method for preparing an anion-exchange membrane of piperidine type with excellent overall performance according to any one of claims 1 to 8, wherein the molar ratio of the 2-bromoethyl acrylate to the styrene compound is 1:1, and the ratio of bromine atoms in the 2-bromoethyl acrylate to the N-methylpiperidine is N Br :n Pip =1:1.2-1:1.6。
10. The piperidine anion-exchange membrane with excellent comprehensive performance is characterized by being prepared by the preparation method of the piperidine anion-exchange membrane with excellent comprehensive performance as claimed in any one of claims 1 to 9.
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