CN115536885A - Preparation method of submicron phase separation anion exchange membrane - Google Patents
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Abstract
The invention provides a preparation method of a submicron phase separation anion exchange membrane, belonging to the technical field of membranes; the invention skillfully introduces aryl olefin compounds into a main chain of a polyaromatic hydrocarbon piperidine polymer by a one-pot method for the first time; the prepared anion-exchange membrane has a remarkable hydrophilic/hydrophobic submicron phase separation structure (1.8 nm), thereby showing ultrahigh conductivity up to 261.6mScm ‑2 @90 deg.C; and the material is soaked in 1M KOH solution for 5000 hours at the temperature of 80 ℃, the conductivity loss is only 6.2 percent, and the material shows extremely high chemical stability; in addition, the film also has low water swelling and good mechanical propertiesPerformance, suitable for alkaline fuel cells, and exhibiting excellent cell performance, peak power density up to 1.8W/cm 2 (ii) a The one-pot method adopted by the method is simple and efficient, and the prepared submicron phase separation anion exchange membrane can be used in the fields of alkaline fuel cells, electrodialysis, organic electrosynthesis, carbon dioxide catalytic reduction, alkaline electrolyzed water and the like.
Description
1. The technical field is as follows:
the invention belongs to the technical field of membranes, and particularly relates to a preparation method of a submicron phase separation anion exchange membrane.
2. Background art:
the hydrogen fuel cell technology has the outstanding advantages of 2-3 times higher energy conversion efficiency, extremely high energy density (120 MJ/kg) and zero pollution than an internal combustion engine, and is one of the most potential ways of coping with global warming problems and realizing the goals of carbon peak reaching and carbon neutralization. Currently, proton exchange membrane fuel cells are most widely used in the field of electric automobiles, but the proton exchange membrane fuel cells excessively depend on expensive noble metal platinum catalysts, so that the disadvantage of high cost is caused. In contrast, basic anion exchange membrane fuel cells can use non-noble metal catalysts, have a greater potential for low cost, and are receiving widespread attention. The anion exchange membrane, as one of its key components, largely determines the performance of the alkaline fuel cell. This requires that the anion exchange membranes have both high conductivity, good mechanical and chemical stability.
At present, a great deal of research aiming at the anion exchange membrane with high conductivity and good chemical stability at home and abroad shows that the development of the polymer main chain without aromatic ether bond is the main strategy for improving the conductivity and the chemical stability of the anion exchange membrane. Among them, the anion exchange membrane of the polymer main chain without aromatic ether bond is best represented by the performances of the main chains of the paraffin and the aromatic. For example, the polynorbornene anion exchange membrane not only has ultrahigh conductivity (212 mS/cm @80 ℃) and excellent alkali resistance stability (1000h @80 ℃) but also has excellent fuel cell performance (3.5W/cm @) 2 ). However, the polymer adopts a relatively complex block polymerization method, the film forming property of The single polyelectrolyte is poor, the polymer needs to be compounded with porous PTFE to form a film, and The preparation process is complicated (Journal of The Electrochemical Society,2020 167 054501). The anion exchange membrane with the polyarylpiperidine main chain also has high conductivity, good chemical stability and excellent fuel cell performance; and also, a method of super acidic catalytic polymerization which is easy to carry out, has a good film-forming property and a high mechanical strength, and has attracted attention (Journal of The Electrochemical Society,166 (7) F3305-F3310 (2019)). The scheme that the main chain structure of polyaromatic hydrocarbon piperidine is changed through the design of the chemical structure of a polymer to obtain more excellent membrane performance is embodied in Chinese patent 'an anion exchange membrane containing a flexible chain segment and based on the polymerization of piperidone and aromatic hydrocarbon, and a preparation method and application thereof' (Special for China)The application No.: 202010903735.0) in a polyarenepiperidine anion exchange membrane.
3. The invention content is as follows:
the invention aims to provide a preparation method of a submicron phase separation anion exchange membrane aiming at the defects of low conductivity, poor chemical stability and the like of the existing anion exchange membrane. The invention skillfully introduces aryl olefin compounds into a main chain of a polyaromatic hydrocarbon piperidine polymer by adopting a one-pot method for the first time. As the aryl olefin compound can simultaneously carry out cationic polymerization and super acid-catalyzed polycondensation in a super acid system, and the cationic polymerization rate is far faster than that of the super acid-catalyzed polycondensation. The prepared anion exchange membrane has a remarkable hydrophilic/hydrophobic submicron phase separation structure (1.8 nm), which not only obviously improves the ionic conductivity, but also enhances the chemical stability. Alkaline fuel cells based on the anion exchange membranes and ionomers prepared exhibit excellent fuel cell performance.
The purpose of the invention is realized as follows:
a submicron phase separated anion exchange membrane is prepared by introducing aryl olefin compounds into a polyaromatic hydrocarbon piperidine main chain to synthesize a novel copolymer, and the chemical structure of the novel copolymer comprises the following repeated structural units:
wherein Ar1 is an aryl moiety of an arylalkenyl compound, ar2 is an aromatic compound, and M-represents I-, cl-, or OH - 、Br - 、HCO 3 2- X is the mole percentage of Ar1 in the copolymer, and x is any number between 0 and 100;
further, the chemical structure of the aryl olefin compound is one or more of the following:
ar2 is one or more of the following groups:
a preparation method of a submicron phase separation anion exchange membrane comprises the following specific steps:
(1) Firstly, mixing the monomers of Ar1 and Ar2 in a ratio of 5: 95-60: adding 40 mol percent of the mixture into dichloromethane, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1 to 1.3, the concentration of the sum of all monomers in the solution is 10 to 50 weight percent;
(2) Sequentially dripping trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in step (1) at the temperature of-10 ℃, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to dichloromethane in the solution is (1-5): 5 to 10:5 to 20, and then reacting for 5 to 24 hours at the temperature; then precipitating in 1-3M KOH solution to obtain polymer solid, washing the polymer solid with pure water for several times, then placing the polymer solid in sufficient 1M potassium carbonate solution at the temperature of 60-80 ℃ for 5-24 h, filtering the solution, washing the polymer solid with pure water for several times, and drying the polymer solid in vacuum at the temperature of 60 ℃ for 24h;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 40-80 ℃, preparing a polymer solution with the solubility of 3-20 wt%, cooling to room temperature, adding methyl iodide with the mass of 1-5 times that of the polymer into the solution, and reacting for 12-48 h; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 50-60 ℃ for 12-24 h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 3-30 wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at the temperature of 60-80 ℃ for 8-24 h to form a film; soaking the dried membrane in 1M KOH at 60 ℃ for 12-48 h, washing the residual KOH with pure water, taking out the membrane, placing the membrane at 50 ℃ for vacuum drying and storing for later use, and preparing a hydroxide-form submicron phase separation anion exchange membrane;
wherein the polar solvent in the step (3) is one or more of tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
after the technical scheme is adopted, the invention mainly has the following advantages:
(1) The prepared anion-exchange membrane has a remarkable submicron phase separation structure, so that ultrahigh conductivity (261.6 mS cm) is achieved -2 @90 deg.C.) and alkali resistance stability (5000 h conductivity loss of 6.2% in 1M KOH solution at 80 deg.C.).
(2) The anion exchange membrane separated by submicron phase has low water absorption swelling capacity and high mechanical strength, and is suitable for alkaline fuel cell application.
(3) Based on the prepared submicron phase separation anion exchange membrane, the fuel cell has excellent performance, and the peak power density reaches up to 1.8W/cm 2 。
The one-pot method adopted by the method is simple and efficient, and the prepared submicron phase separation anion exchange membrane can be applied to the fields of alkaline fuel cells, electrodialysis, organic electrosynthesis, carbon dioxide catalytic reduction, alkaline electrolyzed water and the like. (availability)
4. Description of the drawings:
FIG. 1 is a SAXS diagram of anion exchange membranes prepared in examples 1-4 and a comparative example;
FIG. 2 is a graph of the conductivity versus temperature for anion exchange membranes prepared in examples 1-4 and comparative example;
FIG. 3 is a plot of conductivity versus time for a sub-micron phase separated anion exchange membrane prepared in example 2, under test conditions of 1MKOH,80 ℃;
FIG. 4 is a power curve and I-V plot for a submicron phase separated anion exchange membrane fuel cell prepared in example 2, the fuel being pure hydrogen and the oxidant being pure oxygen and air, respectively (no CO) 2 ) The battery temperature is 80 ℃;
FIG. 5 shows the chemical structure of the submicron phase separation anion exchange membrane.
5. The specific implementation mode is as follows:
the present invention will be further described with reference to the following specific embodiments.
Example 1
A preparation method of a submicron phase separation anion exchange membrane comprises the following specific steps:
(1) Firstly, mixing Ar1 and Ar2 monomers in a ratio of 5:95 mol percent of the mixture is added into dichloromethane and evenly stirred; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1.3, the concentration of the sum of all monomers in the solution is 10wt%;
(2) And (2) sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in step (1) at-4 ℃, wherein the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid to dichloromethane in the solution is 1:10:20, and then reacting for 12 hours at the temperature; then precipitating in 1M KOH solution to obtain polymer solid, washing with pure water for several times, placing in sufficient 1M potassium carbonate solution at 60 ℃ for 5 hours, filtering, washing with pure water for several times, and vacuum-drying the polymer solid at 60 ℃ for 24 hours;
(3) Dissolving the polymer solid dried in the step (2) in a polar solvent at 40 ℃, preparing a polymer solution with the solubility of 10wt%, cooling to room temperature, adding methyl iodide with the mass 2 times that of the polymer into the solution, and reacting for 12 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 60 ℃ for 12h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 10wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 60 ℃ for 8 hours to form a film; soaking the dried membrane in 1M KOH at 60 deg.C for 48h, washing the residual KOH with pure water, taking out the membrane, vacuum drying at 50 deg.C, and storing to obtain hydroxide-type submicron phase separation anion exchange membrane;
(4) Anion exchange membrane performance testing
And (3) testing the film appearance: testing the phase structure of the anion-exchange membrane prepared in the step (3) by small-angle X-ray scattering (SAXS) to obtain a curve shown in figure 1;
testing the conductivity of the film: cutting a 1cm × 4cm sample of the anion exchange membrane prepared in the step (3), placing the sample in a 1MKOH solution at 60 ℃ for 12h, then washing the sample with deionized water for several times, and testing the sample at different temperatures by using a Solartron 1287 and 1260 alternating current impedance instrument to obtain a curve shown in the figure 2;
testing alkali resistance of the film: cutting a 1cm × 4cm sample of the anion exchange membrane prepared in the step (3), placing the anion exchange membrane in a 1MKOH solution at 80 ℃, and testing the conductivity of the membrane at 20 ℃ at intervals to obtain a sample shown in a figure 3;
(5) Fuel cell performance test
First, an appropriate amount of commercially available 60wt% Pt/C and PtRu/C catalyst and isopropanol were weighed into a sample tube, followed by the addition of an amount of the anion exchange resin solution (5 wt% DMSO solution), and the sample tube was sonicated in a water bath for a period of time to form a catalyst ink. Respectively spraying 60wt% Pt/C and PtRu/C catalyst ink prepared by ultrasonic on two sides of the membrane prepared in the step (3) to form a cathode catalyst layer and an anode catalyst layer, and preparing a fuel Cell Chip (CCM) with the loading capacity of 0.4mg/cm 2 (ii) a Finally, the prepared CCM was assembled in a fuel cell test system (850 e Multi range, scribner Associates Co) for cell performance test. The test conditions were: the temperature of the cell is 80 ℃, pure hydrogen is used as fuel, pure oxygen and air (without CO) 2 ) The test results are shown in the graph of fig. 4 for the oxidant.
Example 2
A preparation method of a submicron phase separation anion exchange membrane comprises the following specific steps:
(1) Firstly, mixing Ar1 and Ar2 monomers in a ratio of 10: adding the mixture into dichloromethane according to the molar ratio of 90, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1.2, the concentration of the sum of all monomers in the solution is 5wt%;
(2) And (2) sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in the step (1) at the temperature of 0 ℃, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to dichloromethane in the solution is 1:10:10, and then reacting for 24 hours at the temperature; then precipitating in 2M KOH solution to obtain polymer solid, washing with pure water for several times, placing in sufficient 1M potassium carbonate solution at 70 ℃ for 10h, filtering, washing with pure water for several times, and vacuum-drying the polymer solid at 60 ℃ for 24h;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 60 ℃, preparing a polymer solution with the solubility of 5wt%, cooling to room temperature, adding methyl iodide with the mass of 1 time of that of the polymer into the solution, and reacting for 24 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 50 ℃ for 24h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 20wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 80 ℃ for 12 hours to form a film; soaking the dried membrane in 1M KOH at 60 deg.C for 36h, washing the residual KOH with pure water, taking out the membrane, vacuum drying at 50 deg.C, and storing to obtain hydroxide-type submicron phase separation anion exchange membrane;
example 3
A preparation method of a submicron phase separation anion exchange membrane comprises the following specific steps:
(1) Firstly, mixing Ar1 and Ar2 monomers in a ratio of 20:80 mol percent of the mixture is added into dichloromethane and evenly stirred; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1.1, the concentration of the sum of all monomers in the solution is 20wt%;
(2) Sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in the step (1) at the temperature of-1 ℃, wherein the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid to dichloromethane in the solution is 1:5:20, and then reacting for 12 hours at the temperature; then precipitating in 3M KOH solution to obtain polymer solid, washing with pure water for several times, placing in sufficient 1M potassium carbonate solution at 55 ℃ for 24 hours, filtering, washing with pure water for several times, and vacuum-drying the polymer solid at 60 ℃ for 24 hours;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 60 ℃, preparing a polymer solution with the solubility of 8wt%, cooling to room temperature, adding methyl iodide with the mass of 1 time of that of the polymer into the solution, and reacting for 48 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 60 ℃ for 8h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 20wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 80 ℃ for 8 hours to form a film; soaking the dried membrane in 1M KOH at 60 deg.C for 24h, washing the residual KOH with pure water, taking out the membrane, vacuum drying at 50 deg.C, and storing to obtain hydroxide-type submicron phase-separated anion exchange membrane;
example 4
A preparation method of a submicron phase separation anion exchange membrane comprises the following specific steps:
(1) Firstly, mixing Ar1 and Ar2 monomers in a ratio of 30: adding the mixture into dichloromethane according to the molar ratio of 70, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1.3, the concentration of the sum of all monomers in the solution is 10wt%;
(2) And (2) sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in the step (1) at the temperature of 4 ℃, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to dichloromethane in the solution is 1:7:8, then reacting for 12h at the temperature; then precipitating in 1M KOH solution to obtain polymer solid, washing with pure water for several times, placing in sufficient 1M potassium carbonate solution at 55 ℃ for 18h, filtering, washing with pure water for several times, and vacuum-drying the polymer solid at 60 ℃ for 24h;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 55 ℃, preparing a polymer solution with the solubility of 10wt%, cooling to room temperature, adding methyl iodide with the mass 2 times that of the polymer into the solution, and reacting for 48 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 60 ℃ for 8h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 10wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 80 ℃ for 8 hours to form a film; soaking the dried membrane in 1M KOH at 60 deg.C for 24h, washing the residual KOH with pure water, taking out the membrane, vacuum drying at 50 deg.C, and storing to obtain hydroxide-type submicron phase-separated anion exchange membrane;
comparative example
Comparative experimental examples an anion exchange membrane of polyaromatic piperidine without Ar1 was selected, and the specific preparation method was as follows:
(1) Firstly, dissolving an Ar2 monomer in dichloromethane at normal temperature, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of Ar2 to N-methyl-4-piperidone monomer is 1:1.3, the concentration of the sum of all monomers in the solution is 10wt%;
(2) And (2) sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in the step (1) at the temperature of 3 ℃, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to dichloromethane in the solution is 1:8:8, then reacting for 12h at the temperature; then precipitating in 1M KOH solution to obtain polymer solid, washing with pure water for several times, placing in sufficient 1M potassium carbonate solution at 60 ℃ for 5 hours, filtering, washing with pure water for several times, and vacuum-drying the polymer solid at 60 ℃ for 24 hours;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 40 ℃, preparing a polymer solution with the solubility of 10wt%, cooling to room temperature, adding methyl iodide with the mass 2 times that of the polymer into the solution, and reacting for 12 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 60 ℃ for 12h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 10wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 60 ℃ for 8 hours to form a film; soaking the dried membrane in 1M KOH at 60 deg.C for 48h, washing the residual KOH with pure water, taking out the membrane, vacuum drying at 50 deg.C, and storing to obtain anion exchange membrane in hydroxyl form for comparison;
test results of the present invention:
according to the invention, the aryl olefin compound is successfully introduced into the polyaromatic hydrocarbon piperidine polymer, the cation polymerization and the super acid catalytic polycondensation are effectively combined by skillfully utilizing a one-pot method, and the prepared anion exchange membrane has a 1.8nm obvious submicron phase separation structure, so that the ultra-high conductivity is shown, and the conductivity is as high as 261.6mS cm -2 @90 ℃ and has extremely excellent alkali resistance stability of 5000 h; meanwhile, the anion-exchange membrane prepared by the invention has lower water absorption and swelling and good mechanical properties, is very suitable for alkaline fuel cells, and shows excellent cell performance, and the power density is as high as 1.8W/cm 2 And has wide application prospect.
Claims (7)
1. A preparation method of a submicron phase separation anion exchange membrane comprises the following specific steps:
(1) Firstly, mixing the monomers of Ar1 and Ar2 in a ratio of 5: 95-60: adding 40 mol percent of the mixture into dichloromethane, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1 to 1.3, the concentration of the sum of all monomers in the solution is 10 to 50 weight percent;
(2) Sequentially dripping trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in step (1) at the temperature of-10 ℃, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to dichloromethane in the solution is (1-5): 5 to 10:5 to 20, and then reacting for 5 to 24 hours at the temperature; then precipitating in 1-3M KOH solution to obtain polymer solid, washing the polymer solid with pure water for several times, then placing the polymer solid in sufficient 1M potassium carbonate solution at the temperature of 60-80 ℃ for 5-24 h, filtering the solution, washing the polymer solid with pure water for several times, and drying the polymer solid in vacuum at the temperature of 60 ℃ for 24h;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 40-80 ℃, preparing a polymer solution with the solubility of 3-20 wt%, cooling to room temperature, adding methyl iodide with the mass of 1-5 times that of the polymer into the solution, and reacting for 12-48 h; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 50-60 ℃ for 12-24 h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 3-30 wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at the temperature of 60-80 ℃ for 8-24 h to form a film; placing the dried membrane in 1M KOH at 60 ℃ for soaking for 12-48 h, then washing the residual KOH with pure water, taking out the membrane, placing the membrane in 50 ℃ for vacuum drying and storing for later use, and preparing a hydroxide-form submicron phase separation anion exchange membrane;
2. the method for preparing a submicron phase-separated anion-exchange membrane according to claim 1, wherein in the step (1), the monomers of Ar1 and Ar2 are introduced into the main chain of polyaromatic piperidine by a one-pot method to synthesize a novel copolymer, the chemical structure of which comprises the following repeating structural units:
in the formula, M - Represents I - 、Cl - 、OH - 、Br - 、HCO 3 2- X is the mole percentage of Ar1 in the copolymer, and x is any number between 0 and 100; further, ar1 is an aryl moiety of an arylalkene compound, and the chemical structure of the arylalkene compound is one or more of the following:
ar2 is one or more of the following groups:
3. the method of claim 1, wherein said polar solvent of step (3) is one or more of tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide;
4. the process for the preparation of a submicron phase separated anion exchange membrane according to claim 1, wherein the steps (1), (2) and (3) of the specific preparation process are as follows:
(1) Firstly, mixing Ar1 and Ar2 monomers in a ratio of 5: adding the mixture into dichloromethane according to the molar ratio of 95, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1.3, the concentration of the sum of all monomers in the solution is 10wt%;
(2) And (2) sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in step (1) at-4 ℃, wherein the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid to dichloromethane in the solution is 1:10:20, and then reacting for 12 hours at the temperature; then precipitating in 1M KOH solution to obtain polymer solid, washing with pure water for several times, placing in sufficient 1M potassium carbonate solution at 60 ℃ for 5 hours, filtering, washing with pure water for several times, and vacuum-drying the polymer solid at 60 ℃ for 24 hours;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 40 ℃, preparing a polymer solution with the solubility of 10wt%, cooling to room temperature, adding methyl iodide with the mass 2 times that of the polymer into the solution, and reacting for 12 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 60 ℃ for 12h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 10wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 60 ℃ for 8 hours to form a film; soaking the dried membrane in 1M KOH at 60 deg.C for 48h, washing the residual KOH with pure water, taking out the membrane, vacuum drying at 50 deg.C, and storing to obtain hydroxide-type submicron phase separation anion exchange membrane;
5. the process for the preparation of a submicron phase separated anion exchange membrane according to claim 1, wherein the steps (1), (2) and (3) of the specific preparation process are as follows:
(1) Firstly, mixing Ar1 and Ar2 monomers in a ratio of 10: adding the mixture into dichloromethane according to the molar ratio of 90, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1.2, the concentration of the sum of all monomers in the solution is 5wt%;
(2) And (2) sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in the step (1) at the temperature of 0 ℃, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to dichloromethane in the solution is 1:10:10, and then reacting for 24 hours at the temperature; then precipitating in 2M KOH solution to obtain polymer solid, washing with pure water for several times, placing in sufficient 1M potassium carbonate solution at 70 ℃ for 10h, filtering, washing with pure water for several times, and vacuum-drying the polymer solid at 60 ℃ for 24h;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 60 ℃, preparing a polymer solution with the solubility of 5wt%, cooling to room temperature, adding methyl iodide with the mass of 1 time of that of the polymer into the solution, and reacting for 24 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 50 ℃ for 24h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 20wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 80 ℃ for 12 hours to form a film; soaking the dried membrane in 1M KOH at 60 deg.C for 36h, washing the residual KOH with pure water, taking out the membrane, vacuum drying at 50 deg.C, and storing to obtain hydroxide-type submicron phase-separated anion exchange membrane;
6. the process for the preparation of a submicron phase separated anion exchange membrane according to claim 1, wherein the steps (1), (2) and (3) of the specific preparation process are as follows:
(1) Firstly, mixing Ar1 and Ar2 monomers in a ratio of 20: adding 80 mol percent of the mixture into dichloromethane, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1.1, the concentration of the sum of all monomers in the solution is 20wt%;
(2) And (2) sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in step (1) at-1 ℃, wherein the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid to dichloromethane in the solution is 1:5:20, and then reacting for 12 hours at the temperature; then precipitating in 3M KOH solution to obtain polymer solid, washing with pure water for a plurality of times, placing in sufficient 1M potassium carbonate solution for 24 hours at the temperature of 55 ℃, filtering, washing with pure water for a plurality of times again, and drying the polymer solid in vacuum for 24 hours at the temperature of 60 ℃;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 60 ℃, preparing a polymer solution with the solubility of 8wt%, cooling to room temperature, adding methyl iodide with the mass of 1 time of that of the polymer into the solution, and reacting for 48 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and performing vacuum drying for 8 hours at the temperature of 60 ℃ to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 20wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 80 ℃ for 8h to form a film; soaking the dried membrane in 1M KOH at 60 deg.C for 24h, washing the residual KOH with pure water, taking out the membrane, vacuum drying at 50 deg.C, and storing to obtain hydroxide-type submicron phase separation anion exchange membrane;
7. the process for the preparation of a submicron phase separated anion exchange membrane according to claim 1, wherein the steps (1), (2) and (3) of the specific preparation process are as follows:
(1) Firstly, mixing Ar1 and Ar2 monomers in a ratio of 30: adding the mixture into dichloromethane according to the molar ratio of 70, and uniformly stirring; adding N-methyl-4-piperidone monomer into the solution, and stirring for dissolving; the molar ratio of the sum of Ar1 and Ar2 monomers to the N-methyl-4-piperidone monomer is 1:1.3, the concentration of the sum of all monomers in the solution is 10wt%;
(2) And (2) sequentially dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in the step (1) at the temperature of 4 ℃, wherein the volume ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid to dichloromethane in the solution is 1:7:8, then reacting for 12h at the temperature; then precipitating in 1M KOH solution to obtain polymer solid, washing with pure water for several times, placing in sufficient 1M potassium carbonate solution at 55 ℃ for 18h, filtering, washing with pure water for several times, and vacuum-drying the polymer solid at 60 ℃ for 24h;
(3) Dissolving the polymer solid obtained after vacuum drying in the step (2) in a polar solvent at 55 ℃, preparing a polymer solution with the solubility of 10wt%, cooling to room temperature, adding methyl iodide with the mass 2 times that of the polymer into the solution, and reacting for 48 hours; dropwise adding the reacted polymer solution into ethyl acetate for precipitation, filtering, washing with ethyl acetate for several times, and vacuum-drying at 60 ℃ for 8h to obtain the resin; finally, dissolving the resin in a polar solution to prepare a resin homogeneous solution with the concentration of 10wt%, casting the resin homogeneous solution on a glass plate, and drying the glass plate at 80 ℃ for 8 hours to form a film; and then placing the dried membrane in 1M KOH and soaking at 60 ℃ for 24h, washing residual KOH with pure water, taking out the membrane, placing the membrane in 50 ℃ for vacuum drying and storing for later use, and preparing the hydroxide-form submicron phase separation anion exchange membrane.
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| US20190036143A1 (en) * | 2016-03-28 | 2019-01-31 | University Of Delaware | Poly(aryl piperidinium) polymers for use as hydroxide exchange membranes and ionomers |
| CN113851683A (en) * | 2021-08-27 | 2021-12-28 | 重庆大学 | Preparation method of carbazole polyaromatic hydrocarbon piperidine anion exchange membrane |
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| US20190036143A1 (en) * | 2016-03-28 | 2019-01-31 | University Of Delaware | Poly(aryl piperidinium) polymers for use as hydroxide exchange membranes and ionomers |
| CN113851683A (en) * | 2021-08-27 | 2021-12-28 | 重庆大学 | Preparation method of carbazole polyaromatic hydrocarbon piperidine anion exchange membrane |
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| CN117024924A (en) * | 2023-10-08 | 2023-11-10 | 佛山科学技术学院 | Ultralow-swelling anti-free radical polyaryl anion exchange membrane and preparation method thereof |
| CN117024924B (en) * | 2023-10-08 | 2024-01-26 | 佛山科学技术学院 | Ultralow-swelling anti-free radical polyaryl anion exchange membrane and preparation method thereof |
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