CN110694491A - Nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material and preparation method and application thereof - Google Patents
Nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material and a preparation method thereof. The preparation method disclosed by the invention is simple, rapid and safe to operate, and the prepared alkaline membrane material has the characteristics of controllable structure, high ion exchange capacity, high conductivity, excellent mechanical property, good alkali stability and the like, can meet the requirements of the fields of fuel cells, electrolyzed water and the like, and has a good development prospect.
Description
Technical Field
The invention belongs to the field of polymer design and synthesis of fuel cells and electrolytic water film materials, and particularly relates to a nitrogen-containing heterocyclic quaternary ammonium salt anion exchange film material and a preparation method and application thereof.
Background
In order to overcome the difficulties of energy crisis and environmental pollution at present and enhance the development of clean energy and renewable energy, hydrogen is used as a clean secondary energy carrier and becomes a bridge for connecting the renewable energy and the traditional fossil energy, and fuel cells and water electrolysis hydrogen production technologies are widely concerned worldwide.
Fuel cells, which are devices capable of directly converting chemical energy of hydrogen energy of fuel into electric energy, have advantages such as high energy conversion efficiency and environmental friendliness, and are considered as next-generation ideal power sources and power cells, and have attracted attention in recent years. Compared with proton exchange membrane fuel cells, anion exchange membrane fuel cells exhibit unique advantages due to their alkaline operating environment: 1) the redox kinetics of the cathode under alkaline conditions are faster than in an acidic environment; 2) non-noble metal catalysts (such as Ag, Ni and the like) can be used, so that the cost of the battery can be greatly reduced; 3) due to OH−The fuel leakage rate (such as methanol and the like) is greatly reduced due to the fact that the fuel transmission direction is opposite to the fuel transmission direction; 4) the alkaline medium is less corrosive to the interior of the cell. Due to the advantages of anion exchange membranesThe technology of hydrogen production by water electrolysis for satisfying the supply of hydrogen energy and anion exchange membranes has also received wide attention.
Anion Exchange Membranes (AEMs) are used as the core component of alkaline anion exchange membrane electrochemical devices, primarily to block electrodes and conduct OH−The performance level of the fuel cell directly influences the energy conversion efficiency, the service life and other performance indexes of the fuel cell. However, compared with the mature proton exchange polymer membrane, the research level of the basic anion exchange polymer membrane is relatively lagged, and some problems to be solved still exist, such as poor chemical stability and short service life. From the practical application requirements, the anion exchange polymer membrane suitable for the alkaline anion exchange membrane electrochemical device not only needs to have excellent mechanical properties, low swelling ratio and good thermal stability, but also needs to meet the conditions of high conductivity, excellent chemical stability and the like.
Trimethylamine Quaternary Ammonium Salt (QAs) -based anion exchange membranes commonly used in anion exchange membranes can degrade in certain alkaline environments, particularly at higher temperatures, resulting in loss of ionic groups and undesirable degradation of the polymer backbone. The presently accepted mechanism of cationic degradation of quaternary ammonium salts is mainly hofmann elimination, direct nucleophilic substitution, ylide intermediate formation or other rearrangement reactions. An effective alternative is to add other stable organic cations to the preparation of the AEMs polymers. The basic stability of 26 different quaternary ammonium cations was studied by Marino and Kreuer, and it was found that the basic stability of azacyclic quaternary ammonium cations is exceptionally good due to their inherent ring strain, which is detrimental to nucleophilic substitution and elimination reactions.
In recent years, nitrogen heterocyclic quaternary ammonium cations have attracted much attention because of their outstanding alkali resistance, and therefore nitrogen heterocyclic quaternary ammonium cations are expected to solve the problem of low lifetime of the existing basic anion exchange membranes. However, how to graft the nitrogen-containing heterocyclic quaternary ammonium cation onto the polymer main chain and develop an alkaline anion exchange membrane with high ionic conductivity, high alkali resistance and high device tolerance is a technical problem which needs to be solved urgently in the technical field.
Disclosure of Invention
The invention aims to provide a nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material with higher alkali stability and longer device service life, a method for preparing the anion exchange membrane material by using click chemistry and application of the material.
The invention adopts the following technical scheme:
a nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material has a general formula:
wherein x is the degree of substitution, and x is more than 0 and less than or equal to 100;
R1is a full carbon chain or a carbon chain containing an ether oxygen bond, and the total length is 1 to 12 carbon atoms;
R2is a full carbon chain or a carbon chain containing an ether oxygen bond, and the total length is 1 to 12 carbon atoms;
R1，R2the same or different;
R3is nitrogen heterocyclic quaternary ammonium salt cation.
In the above nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material, R is3Is one of the following structures;
wherein R is4，R5Is a carbon chain with 1-4 carbon atoms or an ether oxygen bond and isopropylidene, R4And R5May be the same or different;
r is-H, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2Or- (CH)3)2；
R' is-CH3、-OCH3、-OCH2CH3、-CF3、-OCF3or-OH.
A preparation method of the nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material comprises the following steps:
(1) synthesis and preparation of quaternary ammonium salt cation of alkynyl-terminated nitrogen-containing heterocycle through Ohira-Bestmann and Menschutkin reaction
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(2) Modifying a polymer framework with chloromethyl and bromomethyl with the degree of substitution x or an alkyl chain containing chloromethyl and bromomethyl by chloromethylation, bromomethylation, lithium chemistry, Grignard reaction or reduction operation after friedel-crafts acylation;
(3) dissolving the synthesized polymer containing the halogenated methyl group in an organic solvent, adding sodium azide according to 1 ~ 10 equivalent times of the molar quantity of the halogenated methyl in the polymer, and reacting for 24 ~ 72h at the temperature of 20 ~ 100 ℃ to obtain a methyl azide polymer;
(4) dissolving the methyl azide polymer with the substitution degree of x prepared in the step (3) in an organic solvent in a Schlenk flask, sequentially adding the alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation, the organic ligand and the halogenated cuprous salt prepared in the step (1) according to a certain proportion, degassing through three times of freezing-unfreezing circulation, placing in vacuum, stirring in an oil bath at 50 ~ 80 ℃ for 24 ~ 72h, precipitating the mixture into a poor solvent, washing with water for three times, and drying in vacuum at 50 ~ 70 ℃ for 24 ~ 48h to obtain the copolymer grafted with the nitrogen-containing heterocyclic quaternary ammonium salt group;
(5) dissolving the copolymer grafted with the nitrogen heterocyclic quaternary ammonium salt group prepared in the step (4) in an organic solvent to prepare a casting solution with the mass fraction of 7 ~ 15 wt%, then casting the casting solution on plate glass, drying the plate glass at 30 ~ 100 ℃ for 24 h, and then drying the plate glass in vacuum at 50 ~ 60 ℃ for 24 h;
(6) and (3) soaking the membrane material obtained in the step (5) in an alkaline solution at 30 ~ 50 ℃ for 24 ~ 48h to convert anions in the membrane into hydroxide radicals, thus obtaining the nitrogen heterocyclic ring quaternary ammonium salt anion exchange membrane material.
In the preparation method, the polymer skeleton is one of polyphenyl ether, polystyrene, polysulfone, polyether ether ketone, poly (styrene-b-isobutylene-b-styrene), hydrogenated styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer or biphenyl type polysulfone.
In the step (3), the step (4) and the step (5) of the preparation method, the organic solvent is one or a mixture of more of tetrahydrofuran, chloroform, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone in any proportion.
In the step (4) of the preparation method, the poor solvent is more than one of benzene, toluene, xylene, acetone and ether.
In the step (4) of the preparation method, the molar ratio of the methyl azide polymer, the alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation, the organic ligand and the halogenated cuprous salt is 1:1.2 ~ 1.5:0.6 ~ 0.75.75: 0.3 ~ 0.38.38.
In the step (4) of the preparation method, the halogenated cuprous salt is more than one of cuprous bromide and cuprous chloride.
In the step (4) of the production method, the organic ligand is at least one of 2, 2' -bipyridine, 1,4,7, 7-pentamethyldiethylenetriamine and 1,1,4,7,10, 10-hexamethyltriethylenetetramine.
In the step (6) of the preparation method, the alkaline solution is 0.5 ~ 1 mol/L sodium hydroxide or potassium hydroxide solution.
An application of the nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material in fuel cells and hydrogen production by water electrolysis.
The invention has the beneficial effects that:
the invention introduces nitrogen heterocyclic quaternary ammonium salt cation with excellent alkali stability into the side chain of the polymer skeleton by using a simple and efficient click chemical modification method, realizes effective regulation and control of the molecular structure of the polymer, and enables functional groups to be far away from the polymer main bodyChain, weakening OH-The degradation of the functional groups caused by the attack of the functional groups improves the alkali resistance of the anion exchange membrane and the tolerance of devices. Meanwhile, the long-term side chain has flexibility, and can form good microscopic hydrophilic-hydrophobic phase separation, thereby improving the ionic conductivity. The invention takes account of the problems of ion conductivity, chemical stability and device service life of the alkaline anion exchange membrane, and has better application prospect in the fields of fuel cells and hydrogen production by water electrolysis.
Drawings
FIG. 1 is a nuclear magnetic spectrum of the anion exchange membrane PPO-DMP-40 prepared in example 2 and the anion exchange membrane PPO-ASU-40 prepared in example 4.
Fig. 2 is a nuclear magnetic spectrum of the anion exchange membrane SCPi prepared in example 5 and the anion exchange membrane LSCPi prepared in example 6.
Fig. 3 is a graph showing initial performance tests of anion exchange membrane fuel cells prepared in example 1 and example 3, respectively.
Fig. 4 is a stability test chart of the anion exchange membrane fuel cells prepared in example 1 and example 3, respectively.
Fig. 5 is a graph showing initial performance tests of anion exchange membrane fuel cells prepared in example 5 and example 6, respectively.
Fig. 6 is a stability test chart of the anion exchange membrane fuel cells prepared in example 5 and example 6, respectively.
Fig. 7 is a test chart of initial performance of electrolyzed water in the process of producing hydrogen by electrolyzing water for anion-exchange membranes prepared in example 5 and example 6 respectively.
Fig. 8 is a test chart of stability of electrolyzed water of the anion-exchange membranes prepared in example 5 and example 6 respectively in a process of producing hydrogen by electrolyzing water.
Detailed Description
The present invention is further described with reference to several embodiments, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention, and the present invention shall be covered thereby.
Example 1
In this embodiment, the chemical structural formula of the alkynyl terminated nitrogen-containing heterocyclic quaternary ammonium salt cation EDMP used for the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry is as follows:
the chemical structural formula of the nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is as follows:
alkynyl-terminated azacyclic quaternary ammonium salt cations, 4-ethynyl-1, 1-dimethyl-piperidine iodide (EDMP) by Ohira-Bestmann reaction and subsequentN-tert-butoxycarbonyl (Boc) deprotection and Menschutkin reaction. Polyphenylene Oxide (PPO) with a bromomethyl degree of substitution of 30% (0.80 g, 1.814 mmol azide) was dissolved in 10 mL NMP in a Schlenk flask, followed by the sequential addition of the alkynyl terminated azacyclic cation EDMP (0.577 g, 2.177 mmol), PMDETA (0.227 mL, 1.089 mmol) and CuBr (0.078 g, 0.545 mmol). The flask was degassed by three freeze-thaw cycles and then placed under vacuum and after stirring for 30 h under a 50 ℃ oil bath, the mixture was precipitated into ether and then washed three times with water. Vacuum drying at 60 ℃ for 24 h to obtain the PPO-DMP-30 copolymer with the yield of 90%.
The obtained polymer was formulated into a casting solution with a solid content of 8 wt% using NMP, and then cast on a flat glass, dried at 60 ℃ for 24 hours, and then vacuum-dried at 60 ℃ for 24 hours. After evaporation of the solvent, the glass plate was immersed in deionized water until the film separated from the glass. The membranes in the hydroxide form were made air free by soaking the membranes in the iodide form in 1M NaOH for 48h at 30 ℃ respectively.
Finally, the membrane was thoroughly rinsed with deionized water to remove any residual NaOH. the thickness of the membrane was in the range of 45 ~ 55 μm. the anion exchange membrane material PPO-DMP-30 was obtained by the above method.
Example 2
The chemical structural formula of the alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation EDMP used for the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is the same as that in the embodiment 1.
The chemical structural formula of the nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is the same as that in the embodiment 1.
Alkynyl-terminated azacyclic quaternary ammonium salt cations, 4-ethynyl-1, 1-dimethyl-piperidine iodide (EDMP) by Ohira-Bestmann reaction and subsequentN-tert-butoxycarbonyl (Boc) deprotection and Menschutkin reaction. Polyphenylene Oxide (PPO) with a bromomethyl degree of substitution of 40% (0.80 g, 2.346 mmol azide) was dissolved in 10 mL NMP in a Schlenk flask, followed by the sequential addition of the alkynyl terminated nitrogen heterocyde cations EDMP (0.933 g, 3.519 mmol), PMDETA (0.367 mL, 1.760 mmol) and CuBr (0.126 g, 0.880 mmol). The flask was degassed by three freeze-thaw cycles and then placed under vacuum and after stirring in a 55 ℃ oil bath for 48h, the mixture was precipitated into ether and then washed three times with water. The PPO-DMP-40 copolymer is obtained after vacuum drying for 24 h at the temperature of 60 ℃, and the yield is 93%.
The obtained polymer was formulated into a casting solution with a solid content of 9 wt% using NMP, and then cast on a flat glass, dried at 60 ℃ for 30 hours, and then vacuum-dried at 60 ℃ for 24 hours. After evaporation of the solvent, the glass plate was immersed in deionized water until the film separated from the glass. The membranes in the hydroxide form were made air free by soaking the membranes in the iodide form in 1M NaOH for 48h at 30 ℃ respectively.
Finally, the membrane is thoroughly washed by deionized water to remove any residual NaOH, the thickness of the membrane is in the range of 45 ~ 55 μm, and the anion exchange membrane material PPO-DMP-40 is obtained by the method, and the nuclear magnetic spectrum of the material is shown in figure 1.
Example 3
The chemical structural formula of the alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation EASU used for the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry is as follows:
the chemical structural formula of the nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is as follows:
alkynyl-terminated azacyclic quaternary ammonium salt cations, 3-ethynyl-6-azo-spiro [5.5]Undecane-6-bromide (EASU) by Ohira-Bestmann reaction and subsequentN-tert-butoxycarbonyl (Boc) deprotection and Menschutkin reaction. Polyphenylene Oxide (PPO) with a bromomethyl degree of substitution of 30% (0.80 g, 1.814 mmol azide) was dissolved in 10 mL NMP in a Schlenk flask, and then the alkynyl-terminated azacyclic cation EASU (0.559 g, 2.177 mmol), PMDETA (0.227 mL, 1.089 mmol) and CuBr (0.078 g, 0.545 mmol) were added sequentially. The flask was degassed by three freeze-thaw cycles and then placed under vacuum and after stirring for 30 h under a 50 ℃ oil bath, the mixture was precipitated into ether and then washed three times with water. The PPO-ASU-30 copolymer is obtained after vacuum drying for 24 h at the temperature of 60 ℃, and the yield is 92%.
The obtained polymer is prepared into casting solution with solid content of 8 wt% by DMSO, and then the casting solution is cast on flat glass, dried for 24 h at 60 ℃, and then dried for 24 h under vacuum at 60 ℃. After evaporation of the solvent, the glass plate was immersed in deionized water until the film separated from the glass. The membranes in the hydroxide form were made air free by soaking the membranes in the bromide form in 1M NaOH for 48h at 30 c, respectively.
Finally, the membrane was thoroughly rinsed with deionized water to remove any residual NaOH. the thickness of the membrane was in the range of 45 ~ 55 μm. the anion exchange membrane material PPO-ASU-30 was obtained by the above method.
Example 4
The chemical structural formula of the alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation EASU used for the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is the same as that in the embodiment 3.
The chemical structural formula of the nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is the same as that in the embodiment 3.
Alkynyl-terminated azacyclic quaternary ammonium salt cations, 3-ethynyl-6-azo-spiro [5.5]Undecane-6-bromide (EASU) by Ohira-Bestmann reaction and subsequentN-tert-butoxycarbonyl (Boc) deprotection and Menschutkin reaction. Polyphenylene Oxide (PPO) with a bromomethyl degree of substitution of 40% (0.80 g, 2.346 mmol of azide) was dissolved in 10 mL of NMP in a Schlenk flask, and then the alkynyl-terminated azacyclic cations EASU (0.904 g, 3.519 mmol), PMDETA (0.367 mL, 1.760 mmol) and CuBr (0.126 g, 0.880 mmol) were added sequentially. The flask was degassed by three freeze-thaw cycles and then placed under vacuum and after stirring in a 55 ℃ oil bath for 48h, the mixture was precipitated into ether and then washed three times with water. The PPO-ASU-40 copolymer is obtained after vacuum drying for 24 h at the temperature of 60 ℃, and the yield is 95%.
The obtained polymer is prepared into casting solution with solid content of 8 wt% by DMSO, and then the casting solution is cast on flat glass, dried for 24 h at 60 ℃, and then dried for 24 h under vacuum at 60 ℃. After evaporation of the solvent, the glass plate was immersed in deionized water until the film separated from the glass. The membranes in the hydroxide form were made air free by soaking the membranes in the bromide form in 1M NaOH for 48h at 30 c, respectively.
Finally, the membrane is thoroughly rinsed with deionized water to remove any residual NaOH, the thickness of the membrane is in the range of 45 ~ 55 μm, and the anion exchange membrane material PPO-ASU-40 is obtained by the method, and the nuclear magnetic spectrum of the material is shown in FIG. 1.
Example 5
The chemical structural formula of the alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation PPi used for the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is as follows:
the chemical structural formula of the nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is as follows:
the alkynyl-terminated azacyclo quaternary ammonium salt cation and 1-methyl-1-propynyl piperidine ammonium bromide (PPi) are synthesized by Menschutkin reaction. Polyphenylene Oxide (PPO) with a bromomethyl degree of substitution of 30% (0.80 g, 1.814 mmol azide) was dissolved in 10 mL NMP in a Schlenk flask, and then the alkynyl-terminated azacyclic cations PPi (0.475 g, 2.177 mmol), PMDETA (0.227 mL, 1.089 mmol) and CuBr (0.078 g, 0.545 mmol) were added in that order. The flask was degassed by three freeze-thaw cycles and then placed under vacuum and after stirring in a 50 ℃ oil bath for 24 h, the mixture was precipitated into ether and then washed three times with water. After vacuum drying at 60 ℃ for 24 h, an SCPi copolymer was obtained with a yield of 95%.
The obtained polymer was prepared into a casting solution with a solid content of 10 wt% using DMF, and then cast on flat glass, dried at 60 ℃ for 24 hours, and then vacuum-dried at 60 ℃ for 24 hours. After evaporation of the solvent, the glass plate was immersed in deionized water until the film separated from the glass. The membranes in the hydroxide form were made air free by soaking the membranes in the bromide form in 1M KOH at 30 c for 48h each.
Finally, the membrane was rinsed thoroughly with deionized water to remove any remaining koh-the thickness of the membrane was in the range of 45 ~ 55 μm-the anion exchange membrane material SCPi was obtained by the above method and its nuclear magnetic spectrum is shown in fig. 2.
Example 6
The chemical structural formula of alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation HPi used for the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is as follows:
the chemical structural formula of the nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the embodiment is as follows:
the alkynyl-terminated azacyclo quaternary ammonium salt cation and 1-methyl-1-hexynyl piperidine chloroammonium salt (HPi) are synthesized through a Menschutkin reaction. Polyphenylene Oxide (PPO) with a bromomethyl degree of substitution of 30% (0.80 g, 1.814 mmol azide) was dissolved in 10 mL NMP in a Schlenk flask, and then the alkynyl-terminated azacyclic cations HPi (0.668 g, 2.177 mmol), PMDETA (0.227 mL, 1.089 mmol) and CuBr (0.078 g, 0.545 mmol) were added in that order. The flask was degassed by three freeze-thaw cycles and then placed under vacuum and after stirring in a 55 ℃ oil bath for 24 h, the mixture was precipitated into ether and then washed three times with water. After drying at 60 ℃ for 24 h under vacuum, the LSCPi copolymer was obtained in 94% yield.
The obtained polymer was formulated into casting solution with solid content of 7 wt% with DMSO, and then cast on plate glass, dried at 60 ℃ for 24 h, and then vacuum dried at 60 ℃ for 24 h. After evaporation of the solvent, the glass plate was immersed in deionized water until the film separated from the glass. The membranes in the hydroxide form were made air free by soaking the membranes in the iodide form in 1M KOH at 30 c for 48h each.
Finally, the membrane was rinsed thoroughly with deionized water to remove any remaining koh-the thickness of the membrane was in the range of 45 ~ 55 μm-the anion exchange membrane material LSCPi was obtained by the above method, the nuclear magnetic spectrum of which is shown in fig. 2.
Comparative example
The chemical structural formula of the trimethylamine quaternary ammonium salt anion exchange membrane material prepared by click chemistry in the comparative example is as follows:
in a 100 mL blue-capped bottle, 1 g of polyphenylene oxide (PPO) having a bromomethyl substitution degree of 30% was dissolved in 10 mL of N-methylpyrrolidone (NMP), and then 2.5 mL of an ethanol solution of trimethylamine (4.2 mol/L) was rapidly added thereto, followed by sealing and reacting at 60 ℃ for 24 hours in an oil bath. And removing excessive trimethylamine and ethanol from the reaction solution by using a rotary evaporator, precipitating the product from the residual reaction solution by using diethyl ether, and naturally airing.
The obtained polymer BTMA was formulated into a casting solution with a solid content of 8 wt% using NMP, and then cast on a flat glass, dried at 60 ℃ for 24 hours, and then vacuum-dried at 60 ℃ for 24 hours. After evaporation of the solvent, the glass plate was immersed in deionized water until the film separated from the glass. The membranes in the hydroxide form were made air free by soaking the bromide ion membranes in 1M NaOH at 30 ℃ for 48h, respectively.
Finally, the membrane was rinsed thoroughly with deionized water to remove any residual naoh the thickness of the membrane was in the range of 45 ~ 55 μm.
Examples of effects
The anion exchange membrane materials prepared in example 1 ~ 6 and the comparative example were subjected to the relevant performance tests, and the test results are shown in table 1.
As can be seen from Table 1, the prepared nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane has high ionic conductivity, excellent initial performance and mechanical performance of a fuel cell, and the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane disclosed by the invention can be predicted to have good application prospects.
Table 1 relevant performance test results for examples 1-6 and comparative anion exchange membranes
Application example
The anion exchange membrane containing nitrogen heterocyclic quaternary ammonium salt prepared in example 1 ~ 6 is used as a polyelectrolyte membrane for preparing an alkaline anion exchange membrane fuel cell, the initial performance and stability test of the anion exchange membrane fuel cell prepared in example 1 and example 3 are respectively shown in fig. 3 and fig. 4, and the initial performance and stability test of the anion exchange membrane fuel cell prepared in example 5 and example 6 are respectively shown in fig. 5 and fig. 6.
The nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane prepared in example 1 ~ 6 is used as an electrolyte membrane for hydrogen production by water electrolysis, wherein the initial performance and stability test of water electrolysis in the hydrogen production process by water electrolysis in examples 5 and 6 are respectively shown in fig. 7 and 8.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A nitrogen heterocyclic quaternary ammonium salt anion exchange membrane material is characterized in that the general formula is as follows:
wherein x is the degree of substitution, and x is more than 0 and less than or equal to 100;
R1，R2is a full carbon chain or a carbon chain containing an ether oxygen bond, and the total length is 1 to 12 carbon atoms;
R3is nitrogen heterocyclic quaternary ammonium salt cation.
2. The nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material of claim 1, wherein R is3Is one of the following structures;
wherein R is4，R5Is carbon chain with 1-4 carbon atoms or carbon chain containing ether oxygen bond and isopropylidene;
r is-H, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2Or- (CH)3)2；
R' is-CH3、-OCH3、-OCH2CH3、-CF3、-OCF3or-OH.
3. A method for preparing the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material according to claim 1 or 2, which comprises the following steps:
(1) synthesis and preparation of quaternary ammonium salt cation of alkynyl-terminated nitrogen-containing heterocycle through Ohira-Bestmann and Menschutkin reaction
；
(2) Modifying a polymer framework with chloromethyl and bromomethyl with the degree of substitution x or an alkyl chain containing chloromethyl and bromomethyl by chloromethylation, bromomethylation, lithium chemistry, Grignard reaction or reduction operation after friedel-crafts acylation;
(3) dissolving the synthesized polymer containing the halogenated methyl group in an organic solvent, adding sodium azide according to 1 ~ 10 equivalent times of the molar quantity of the halogenated methyl in the polymer, and reacting for 24 ~ 72h at the temperature of 20 ~ 100 ℃ to obtain a methyl azide polymer;
(4) dissolving the methyl azide polymer with the substitution degree of x prepared in the step (3) in an organic solvent, then sequentially adding the alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation prepared in the step (1), an organic ligand and a halogenated cuprous salt, degassing by three times of freezing-unfreezing circulation, then placing in vacuum, stirring in an oil bath at 50 ~ ℃ for 24 3672 h, precipitating the mixture into a poor solvent, then washing with water for three times, and vacuum-drying at 50 ~ ℃ for 24 ~ h to obtain the copolymer grafted with the nitrogen-containing heterocyclic quaternary ammonium salt group;
(5) dissolving the copolymer grafted with the nitrogen heterocyclic quaternary ammonium salt group prepared in the step (4) in an organic solvent to prepare a casting solution with the mass fraction of 7 ~ 15 wt%, then casting the casting solution on plate glass, drying the plate glass at 30 ~ 100 ℃ for 24 h, and then drying the plate glass in vacuum at 50 ~ 60 ℃ for 24 h;
(6) and (3) soaking the membrane material obtained in the step (5) in an alkaline solution at 30 ~ 50 ℃ for 24 ~ 48h to convert anions in the membrane into hydroxide radicals, thus obtaining the nitrogen heterocyclic ring quaternary ammonium salt anion exchange membrane material.
4. The method of claim 3, wherein the polymer backbone is one of polyphenylene ether, polystyrene, polysulfone, polyetheretherketone, poly (styrene-b-isobutylene-b-styrene), hydrogenated styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, or biphenyl type polysulfone.
5. The preparation method according to claim 3, wherein in the step (3), the step (4) and the step (5), the organic solvent is one or a mixture of several of tetrahydrofuran, chloroform, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone in any proportion.
6. The method according to claim 3, wherein the poor solvent in the step (4) is one or more selected from benzene, toluene, xylene, acetone, and diethyl ether.
7. The preparation method according to claim 3, wherein in the step (4), the molar ratio of the methyl azide polymer to the alkynyl-terminated nitrogen-containing heterocyclic quaternary ammonium salt cation to the organic ligand to the halogenated cuprous salt is 1:1.2 ~ 1.5.5: 0.6 ~ 0.75.75: 0.3 ~ 0.38.38.
8. The process according to claim 3, wherein in the step (4), the cuprous halide salt is one or more selected from cuprous bromide and cuprous chloride.
9. The process according to claim 3, wherein in the step (4), the organic ligand is at least one selected from the group consisting of 2, 2' -bipyridine, 1,4,7, 7-pentamethyldiethylenetriamine and 1,1,4,7,10, 10-hexamethyltriethylenetetramine.
10. Use of the nitrogen-containing heterocyclic quaternary ammonium salt anion exchange membrane material of claim 1 or 2 in fuel cells and hydrogen production by electrolysis of water.
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