CN119133543B - High-temperature proton exchange membrane based on basic group grafted polyvinyl alcohol and preparation method thereof - Google Patents
High-temperature proton exchange membrane based on basic group grafted polyvinyl alcohol and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature proton exchange membrane based on basic group grafted polyvinyl alcohol and a preparation method thereof. The method comprises the steps of taking polyvinyl alcohol as a base material, grafting three compounds with alkaline groups on polyvinyl alcohol side chains through aldol condensation reaction and crosslinking to obtain a polyvinyl alcohol membrane material grafted on the basis of the alkaline groups, and the method comprises the steps of (a) preparing a polyvinyl alcohol solution, (b) adding imidazole formaldehyde or pyridine formaldehyde or halogenated benzaldehyde into the polyvinyl alcohol solution, carrying out reflux reaction by taking an HCl solution as a catalyst to obtain a graft polymer, (c) preparing the graft polymer into a graft membrane, (d) immersing the graft membrane in glutaraldehyde solution for crosslinking, and then adopting a solution casting method to prepare the membrane material, and (e) carrying out phosphoric acid doping on the membrane material. The membrane material has the advantages of lower preparation cost, mild reaction conditions, more compact or more compact structure, transparency, uniformity and compactness, and good conductivity and mechanical property.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a high-temperature proton exchange membrane based on basic group grafted polyvinyl alcohol and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are high-efficiency energy conversion devices that directly convert chemical energy into electrical energy through a polymer membrane as an electrolyte, and are widely used in the fields of electric vehicles, stationary power supplies, and the like. Conventional proton exchange membrane materials such as perfluorosulfonic acid membranes (e.g., nafion series), while exhibiting good proton conductivity at low temperatures, their proton conductivity is moisture dependent, with operating temperatures typically limited to below 80 ℃. This results in a significant decrease in proton conductivity of the membrane when operated at high temperature, and has problems of catalyst poisoning, difficulty in water thermal management, and the like.
In recent years, phosphoric acid doped polymer electrolyte membranes have been attracting attention because of their ability to maintain high proton conductivity in an anhydrous environment, especially polymer and phosphoric acid composites containing basic functional groups. For example, wang Ailian et al, research progress on polybenzimidazole/phosphoric acid doped high temperature proton exchange membranes, mention Polybenzimidazole (PBI) membranes in which the amide group on the imidazole ring in the PBI molecule is a proton acceptor, and proton conduction is accomplished by the N-H bond on the imidazole ring and the phosphate ion. However, the PBI-based membrane material has problems of complicated preparation, high cost, and the like, so that it is an important research direction to develop a low-cost high-performance electrolyte membrane capable of stably operating under anhydrous conditions of 100 ℃ or more.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a high-temperature proton exchange membrane based on basic group grafted polyvinyl alcohol and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A high-temperature proton exchange membrane based on basic group grafted polyvinyl alcohol has the following structural formula:
,
in the general formula, n is a positive integer, and the R structure is any one of the following:
、、。
A preparation method of a high-temperature proton exchange membrane based on basic group grafted polyvinyl alcohol comprises the following steps:
(a) Preparing a polyvinyl alcohol solution by taking a polar organic solvent as a solvent;
(b) Adding imidazole formaldehyde or pyridine formaldehyde or halogenated benzaldehyde into a polyvinyl alcohol solution, adding an HCl solution as a catalyst, stirring and refluxing for reaction, cooling to room temperature after the reaction, pouring the reaction solution into an NaOH aqueous solution to precipitate flocculent fibers, standing, separating, washing and drying to obtain a graft polymer;
(c) Preparing a grafted polymer obtained in the step (b) into a grafted membrane;
(d) Soaking the grafted membrane prepared in the step (c) in glutaraldehyde solution for crosslinking to prepare a membrane material;
(e) And (d) soaking the membrane material prepared in the step (d) in phosphoric acid aqueous solution to carry out phosphoric acid doping, so as to obtain the phosphoric acid doped high-temperature proton exchange membrane.
Further, in the step (a), the polar organic solvent is dimethyl sulfoxide, and the concentration of the polyvinyl alcohol solution is 1-3wt%.
Further, in the stirring reflux reaction system of the step (b), the molar ratio of the added imidazole formaldehyde or pyridine formaldehyde or halogenated benzaldehyde to the polyvinyl alcohol is 1:0.5-1, the concentration of the HCl solution is 37wt%, the dosage ratio of the HCl solution to the polyvinyl alcohol added in the step (a) is 1mL:2g, and the grafting ratio of the grafted polymer is 10-30wt%.
Further, in the step (b), the stirring reflux reaction temperature is 50-60 ℃ and the reaction time is 5-80 h.
Further, the step (c) comprises the steps of dissolving a graft polymer in dimethyl sulfoxide to prepare the graft polymer, pouring the graft polymer solution into a culture dish, evaporating the solvent to dryness, peeling the film from the culture dish, washing and drying to obtain a uniform and transparent film, preparing the graft polymer by taking imidazole formaldehyde or pyridine formaldehyde as a raw material in the step (b), namely preparing the graft polymer by taking halogenated benzaldehyde as a raw material in the step (b), and immersing the obtained film into 1-methylimidazole solution to obtain the uniform and transparent graft film containing imidazole groups.
Further, in the step (C), the grafted polymer is dissolved in dimethyl sulfoxide at the temperature of 75-85 ℃, the concentration of the grafted polymer solution is 1-3 wt%, the solvent evaporation temperature is 60 ℃, the solubility of the 1-methylimidazole solution is 5-15 wt%, and the dosage ratio of the film to the 1-methylimidazole solution is 0.1 g/10 mL.
In the step (d), the concentration of glutaraldehyde solution is 10-30wt%, the dosage ratio of the grafted film to glutaraldehyde solution is 0.1g:15mL, the crosslinking temperature is 25-35 ℃, and the crosslinking time is 0.5-1.5 h.
Further, in the step (e), the concentration of the phosphoric acid aqueous solution is 85wt%, the phosphoric acid doping soaking time is 24-72 h, and the phosphoric acid doping amount of the high-temperature proton exchange membrane is 150-450 wt%.
The beneficial effects of the invention are as follows:
1. The high-temperature proton exchange membrane taking PVA as a matrix has the advantages of easily available raw materials and low cost, and is wide in raw material source, simple and convenient in preparation process and suitable for large-scale industrial production.
2. The proton exchange membrane is prepared by grafting modification of imidazole or pyridine groups and doping of phosphoric acid, and can still keep high proton conductivity at a high temperature (100-180 ℃) under a non-humidifying condition, and the conductivity at 150 ℃ can reach 0.16S/cm at the highest.
3. The membrane material has good stability, namely the membrane material grafted and modified by imidazole or pyridine groups has good mechanical stability and dimensional stability, and can keep lower volume swelling rate and good flexibility under high temperature conditions.
4. The doping content is adjustable, and different phosphoric acid doping amounts (150-450 wt%) of the film material can be realized by adjusting the proportion of the grafted modified imidazole formaldehyde and pyridine formaldehyde (the grafting proportion is 10-30 wt%), so that the application requirements of different proton conductivity requirements are met.
Drawings
FIG. 1 is a graph showing acid doping content, area swelling and volume swelling of the crosslinked films prepared in examples 1 to 6;
FIG. 2 is a graph showing the conductivity of the crosslinked films prepared in examples 1-6 at various temperatures;
FIG. 3 is a graph showing mechanical properties of the crosslinked films prepared in examples 1 to 6;
FIG. 4 shows nuclear magnetic resonance hydrogen spectra of PVA and the graft polymers prepared in example 1 and example 4.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention relates to a preparation method of a composite membrane material based on PVA grafted imidazole formaldehyde and pyridine formaldehyde, which comprises the following steps:
(a) Preparing a polyvinyl alcohol solution, namely stirring and dissolving polyvinyl alcohol (PVA) in a polar organic solvent (preferably dimethyl sulfoxide) at 50-60 ℃ to obtain a polyvinyl alcohol solution with the concentration of 1-3 wt%;
(b) Adding imidazole formaldehyde (preferably 4- (imidazole-1-yl) benzaldehyde) or pyridine formaldehyde (preferably 4-pyridine formaldehyde) or halogenated benzaldehyde (preferably 4- (bromomethyl) benzaldehyde) into a polyvinyl alcohol solution (the molar ratio of imidazole formaldehyde or pyridine formaldehyde or halogenated benzaldehyde to polyvinyl alcohol in the system is 1:0.5-1), adding an HCl solution with the concentration of 37wt% as a catalyst (the dosage ratio of the HCl solution to the polyvinyl alcohol is 1mL:2 g), stirring and refluxing for reaction for 5-80 hours at 50-60 ℃, cooling to room temperature after the reaction, pouring the reaction solution into an NaOH aqueous solution to precipitate flocculent fibers, standing, separating, washing and drying to obtain a grafted polymer with the grafting ratio of 10-30 wt%;
(c) Preparing a grafted film, namely dissolving a grafted polymer in dimethyl sulfoxide (DMSO) at 75-85 ℃ to prepare a 1-3wt% uniform grafted polymer solution, pouring the grafted polymer solution into a Teflon culture dish, placing the Teflon culture dish in a 60 ℃ oven to evaporate the solvent to dryness, peeling, washing and drying the film from the culture dish to obtain a uniform and transparent film, preparing the grafted polymer by taking imidazole formaldehyde or pyridine formaldehyde as a raw material in the step (b), preparing the grafted polymer by taking halogenated benzaldehyde as a raw material in the step (b), completely immersing the obtained film into a 5-15wt% 1-methylimidazole solution (the dosage ratio of the film to the 1-methylimidazole solution is 0.1g:10 mL), and immersing the film at room temperature for 10-15 h to obtain the uniformly and transparent grafted film containing imidazole groups.
(D) Preparing a chemically crosslinked reinforced film, namely immersing the grafted film prepared in the step (C) in glutaraldehyde solution with the concentration of 10-30wt% and crosslinking for 0.5-1.5 h at the temperature of 25-35 ℃ to prepare a film material, wherein the dosage ratio of the grafted film to the glutaraldehyde solution is 0.1g:15mL.
(E) And (3) under the condition of room temperature, soaking the membrane material prepared in the step (d) in a phosphoric acid aqueous solution with the concentration of 85wt% for phosphoric acid doping for 24-72 h, so as to obtain the high-temperature proton exchange membrane with the phosphoric acid doping amount of 150-450 wt%.
The structural formula of the high-temperature proton exchange membrane based on the basic group grafted polyvinyl alcohol prepared by the invention is as follows:
,
in the general formula, n is a positive integer, and the R structure is any one of the following:
、、。
Preferred embodiments are as follows:
Example 1
2G of PVA was added to 45mL of dimethyl sulfoxide at 50℃and stirred until dissolved uniformly. 4- (imidazol-1-yl) benzaldehyde was added at a molar ratio of PVA:4- (imidazol-1-yl) benzaldehyde=1:0.5, 1ml of 37wt% HCl solution was added, and the reaction solution was stirred and refluxed at 50 ℃ for 72 hours, and then cooled to room temperature, and slowly poured into NaOH aqueous solution to precipitate flocculent fibers. After standing, the flocculent fibers were drained and washed 3 times with deionized water. After thorough washing, the polymer was dried for 12 hours to obtain a graft polymer. The grafted polymer was dissolved in DMSO using magnetic stirring at 80 ℃ to form a 2.0 wt% solution. After obtaining a homogeneous solution, a film material was prepared by solution casting, i.e., casting the obtained solution on a teflon petri dish, then evaporating the solvent in a 60 ℃ oven until complete evaporation, then peeling the film from the petri dish, thoroughly washing with deionized water and further drying to obtain a homogeneous transparent grafted film. The graft membrane is soaked in 10 wt percent of GA solution at the temperature of 30 ℃ by taking Glutaraldehyde (GA) as a cross-linking agent for cross-linking for 1 hour (the dosage ratio of the graft membrane to glutaraldehyde solution is 0.1g:15 mL), and the cross-linked and modified membrane material is obtained. The obtained membrane is soaked in 85wt% phosphoric acid water solution for 24 hours at room temperature, and the high temperature proton exchange membrane with 260wt% phosphoric acid doping amount is obtained. The electrical conductivity of the film material under the condition of 150 ℃ and no humidification is 0.117S/cm.
Example 2:
2g of PVA was added to 45mL of dimethyl sulfoxide at 50℃and stirred until dissolved uniformly. 4- (imidazol-1-yl) benzaldehyde was added at a molar ratio of PVA:4- (imidazol-1-yl) benzaldehyde=1:0.5, 1ml of 37wt% HCl solution was added, and the reaction solution was stirred and refluxed at 50 ℃ for 72 hours, and then cooled to room temperature, and slowly poured into NaOH aqueous solution to precipitate flocculent fibers. After standing, the flocculent fibers were drained and washed 3 times with deionized water. After thorough washing, the mixture was dried for 12 hours to obtain a pale yellow product graft polymer. The grafted polymer was dissolved in DMSO using magnetic stirring at 80 ℃ to form a 2.0 wt% solution. After obtaining a homogeneous solution, the membrane material was prepared by solution casting, i.e. casting the solution obtained on a teflon petri dish, then evaporating the solvent in an oven at 60 ℃ until complete evaporation, then peeling the membrane from the petri dish, thoroughly washing with deionized water and further drying to obtain a homogeneous transparent grafted membrane. The grafted membrane is soaked in 20wt% of GA solution at 30 ℃ by taking Glutaraldehyde (GA) as a crosslinking agent to crosslink for 1 hour (the dosage ratio of the grafted membrane to glutaraldehyde solution is 0.1g:15 mL), and the crosslinked and modified membrane material is obtained. The obtained membrane is soaked in 85wt% phosphoric acid water solution for 24 hours at room temperature, and the high temperature proton exchange membrane with 220wt% phosphoric acid doping amount is obtained. The electrical conductivity of the film material under the condition of 150 ℃ and no humidification is 0.158S/cm.
Example 3:
2g of PVA was added to 45mL of dimethyl sulfoxide at 50℃and stirred until dissolved uniformly. 4- (imidazol-1-yl) benzaldehyde was added at a molar ratio of PVA:4- (imidazol-1-yl) benzaldehyde=1:0.5, 1ml of 37wt% HCl solution was added, and the reaction solution was stirred and refluxed at 50 ℃ for 72 hours, and then cooled to room temperature, and slowly poured into NaOH aqueous solution to precipitate flocculent fibers. After standing, the flocculent fibers were drained and washed 3 times with deionized water. After thorough washing, the polymer was dried for 12 hours to obtain a graft polymer. The grafted polymer was dissolved in DMSO using magnetic stirring at 80 ℃ to form a 2.0 wt% solution. After obtaining a homogeneous solution, the membrane material was prepared by solution casting, i.e. casting the solution obtained on a teflon petri dish, then evaporating the solvent in an oven at 60 ℃ until complete evaporation, then peeling the membrane from the petri dish, thoroughly washing with deionized water and further drying to obtain a homogeneous transparent grafted membrane. The graft membrane is soaked in 30 wt% GA solution at 30 ℃ by taking Glutaraldehyde (GA) as a cross-linking agent for cross-linking for 1 hour (the dosage ratio of the graft membrane to glutaraldehyde solution is 0.1g:15 mL), and the cross-linked and modified membrane material is obtained. The obtained membrane is soaked in 85wt% phosphoric acid water solution for 24 hours at room temperature, and the high temperature proton exchange membrane with the phosphoric acid doping amount of 206wt% is obtained. The conductivity of the film material under 150 ℃ non-humidified conditions was 0.094S/cm.
Example 4:
2g of PVA was added to 45mL of dimethyl sulfoxide at 50℃and stirred until dissolved uniformly. 4-pyridinecarbaldehyde was added at a molar ratio of PVA: 4-pyridinecarbaldehyde=1:0.5, 1ml of 37wt% HCl solution was added, and the reaction was stirred at 50 ℃ for 48 hours under reflux, and then the reaction solution was cooled to room temperature, and was slowly poured into NaOH aqueous solution to precipitate flocculent fibers. After standing, the flocculent fibers were drained and washed 3 times with deionized water. After thorough washing, the polymer was dried for 12 hours to obtain a graft polymer. The grafted polymer was dissolved in DMSO using magnetic stirring at 80 ℃ to form a 2.0 wt% solution. After obtaining a homogeneous solution, a film material was prepared by solution casting, i.e., casting the obtained solution on a teflon petri dish, then evaporating the solvent in a 60 ℃ oven until complete evaporation, then peeling the film from the petri dish, thoroughly washing with deionized water and further drying to obtain a homogeneous transparent grafted film. The grafted membrane is soaked in 20 wt% of GA solution at 30 ℃ by taking Glutaraldehyde (GA) as a crosslinking agent to crosslink for 1 hour (the dosage ratio of the grafted membrane to glutaraldehyde solution is 0.1g:15 mL), and the crosslinked and modified membrane material is obtained. The obtained membrane is soaked in 85wt% phosphoric acid water solution for 24 hours at room temperature, and the high temperature proton exchange membrane with 413wt% phosphoric acid doping amount is obtained. The electrical conductivity of the film material under the condition of 150 ℃ and no humidification is 0.163S/cm.
Example 5:
2g of PVA was added to 45mL of dimethyl sulfoxide at 50℃and stirred until dissolved uniformly. 4- (bromomethyl) benzaldehyde was added at a molar ratio of PVA:4- (bromomethyl) benzaldehyde=1:0.5, 1ml of 37wt% HCl solution was added, the reaction solution was stirred at 50 ℃ for reflux reaction for 5 hours, then cooled to room temperature, slowly poured into NaOH aqueous solution to precipitate flocculent fibers, and after standing, the flocculent fibers were discharged and washed with deionized water for 3 times, thoroughly washed, and dried for 12 hours to obtain a graft polymer. The grafted polymer was dissolved in DMSO using magnetic stirring at 80 ℃ to form a 2.0 wt% solution. Then preparing a film material by adopting a solution casting method, namely pouring the reaction solution on a Teflon culture dish, evaporating the solvent in a 60 ℃ oven until the solvent is completely evaporated, peeling the film from the culture dish, thoroughly washing the film by using deionized water and further drying the film to obtain a uniform and transparent film, completely immersing the obtained film in a 10 wt% 1-methylimidazole solution (the dosage ratio of the film to the 1-methylimidazole solution is 0.1g:10 mL), and immersing the film in 12h at room temperature to obtain the uniform and transparent grafted film containing imidazole groups. The grafted membrane is soaked in 20 wt% of GA solution at 30 ℃ by taking Glutaraldehyde (GA) as a crosslinking agent to crosslink for 1 hour (the dosage ratio of the grafted membrane to glutaraldehyde solution is 0.1g:15 mL), and the crosslinked and modified membrane material is obtained. The obtained membrane is soaked in 85wt% phosphoric acid water solution for 24 hours at room temperature, and the high temperature proton exchange membrane with 191wt% phosphoric acid doping amount is obtained. The electrical conductivity of the film material under the condition of 180 ℃ and no humidification is 0.084S/cm.
Example 6:
2g of PVA was added to 45mL of dimethyl sulfoxide at 50℃and stirred until dissolved uniformly. 4- (bromomethyl) benzaldehyde was added at a molar ratio of PVA:4- (bromomethyl) benzaldehyde=1:1, 1ml of 37wt% HCl solution was added, the reaction solution was stirred at 50 ℃ for reflux reaction for 5 hours, then cooled to room temperature, slowly poured into NaOH aqueous solution to precipitate flocculent fibers, and after standing, the flocculent fibers were discharged and washed with deionized water for 3 times, thoroughly washed, and dried for 12 hours to obtain a graft polymer. The grafted polymer was dissolved in DMSO using magnetic stirring at 80 ℃ to form a 2.0 wt% solution. Then the film material is prepared by solution casting, i.e. the reaction solution is poured onto a teflon petri dish, the solvent is evaporated in a 60 ℃ oven until complete evaporation, then the film is peeled off from the petri dish, thoroughly washed with deionized water and further dried to obtain a uniform transparent film. The obtained film was completely immersed in a 10 wt% 1-methylimidazole solution (the ratio of the film to the 1-methylimidazole solution was 0.1g:10 mL), and immersed in 12: 12 h at room temperature to obtain a uniform and transparent grafted film containing imidazole groups. The grafted membrane is soaked in 20 wt% of GA solution at 30 ℃ by taking Glutaraldehyde (GA) as a crosslinking agent to crosslink for 1 hour (the dosage ratio of the grafted membrane to glutaraldehyde solution is 0.1g:15 mL), and the crosslinked and modified membrane material is obtained. The obtained membrane is soaked in 85wt% phosphoric acid water solution for 24 hours at room temperature, and the high temperature proton exchange membrane with 228wt% phosphoric acid doping amount is obtained. The electrical conductivity of the film material under 180 ℃ non-humidified conditions is 0.130S/cm.
The exchange membranes prepared in examples 1-6 were subjected to structural characterization and performance testing. The acid doping content, area swelling and volume swelling of the films prepared in each example are shown in FIG. 1, the conductivity of each film at different temperatures is shown in FIG. 2, the mechanical properties are shown in FIG. 3, and the nuclear magnetic resonance hydrogen spectra of PVA and the graft polymers prepared in example 1 and example 4 are shown in FIG. 4.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
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| CN116813855A (en) * | 2023-06-13 | 2023-09-29 | 中国科学院长春应用化学研究所 | A cross-linked polymer containing high-density imidazole, its preparation method and its application in fuel cells |
| CN118422272A (en) * | 2024-04-19 | 2024-08-02 | 山西国润储能科技有限公司 | Proton acid doped high-performance PEM water electrolysis proton exchange membrane |
| CN118659014B (en) * | 2024-08-15 | 2024-10-29 | 武汉轻工大学 | Anion exchange membrane, preparation method and application thereof |
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| CN111269550A (en) * | 2020-02-15 | 2020-06-12 | 西北工业大学 | Crosslinked anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and preparation method |
Non-Patent Citations (1)
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| Acid catalysed cross-linking of poly vinyl alcohol(PVA) by glutaraldehyde: effect of crosslink density on the characteristics of PVA membranes used in single chambered microbial fuel cells;Ruchira Rudra等;《RSC Advances》;20150925;第5卷;第83436-83447页 * |
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