CN115353657B - Preparation method of magnetic field induced organic-inorganic composite cross-linked anion exchange membrane - Google Patents
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Abstract
The invention relates to the technical field of fuel cells, and particularly discloses a preparation method of a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane, which comprises the following steps: (1) Preparation of hydrotalcite coated ferroferric oxide (Fe) under alkaline condition 3 O 4 @ LDH) nanoparticles; (2) Carrying out ultrasonic dispersion on hydrotalcite coated ferroferric oxide to obtain a dispersion liquid, and dissolving a quaternized polymer to obtain a quaternized polymer solution; (3) Adding inorganic matter dispersion liquid and polyvinyl alcohol solution into quaternized polymer solution, and fully mixing to obtain casting film liquid; (4) Casting the casting solution on a glass plate, then integrally placing the glass plate in a magnetic field environment, carrying out crosslinking reaction, and evaporating the solvent to dryness to obtain the glass plate. The invention takes quaternized polyphenyl ether as an anion exchange membrane matrix, and loads hydrotalcite on Fe 3 O 4 The problem of agglomeration of hydrotalcite can be effectively avoided, and after inorganic magnetic particles are doped, a long-range ordered ion channel can be constructed in the membrane, so that the ion conductivity is improved.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation method of a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane.
Background
The fuel cell is a direct energy conversion device, which mainly comprises two parts, namely an energy source (such as natural gas, hydrogen, ethanol, methanol, formic acid or phosphoric acid and the like) and an oxidant (such as air or oxygen and the like), and can directly convert chemical energy of fuel oxidation into electric energy, and the device has high energy conversion efficiency, low pollution and low noise, and is one of the most promising technologies for generating electricity by using renewable chemical energy. Among the various fuel cells, proton exchange membrane fuel cells have been most widely studied, but the acidic working environment thereof makes it possible to use only noble metals such as platinum catalysts for the cells, resulting in a great increase in cell cost. In turn, the eye is turned to anion exchange membrane fuel cells which exhibit enhanced fuel oxidation and oxygen reduction kinetics in alkaline environments, which allow non-noble metals to be used as active catalysts (e.g., silver and nickel) which greatly reduce production costs, and which are more stable in alkaline media than in acidic media, providing a means to address the high cost and durability of catalysts. As a key component of a fuel cell, an anion exchange membrane is both a conductor of hydroxide ions and a separation barrier for fuel and oxidant. The ideal anion exchange membrane should have high ionic conductivity, excellent mechanical properties, sufficient chemical stability and dimensional stability.
The quaternary ammonium cationization is carried out by obtaining OH from the polymer - One of the main pathways for conductivity. Basic anion exchange membranes with arylene as the backbone have been available in the last decadeIn intensive research, polyphenylene oxide (PPO) is an engineering plastic with good mechanical properties and chemical stability, and can be quaternized after bromination or chloroacetylation, so that other aromatic polymers are avoided from using strong carcinogenic chloromethylation reagents (such as chloromethyl ether), and the PPO is suitable for large-scale production, and has been proved to have better chemical stability under strong alkaline conditions than other polyarylethers (such as polyarylethersulfone), so that the PPO has attracted extensive attention of researchers and industry. However, due to OH - The migration rate of (a) is lower (compared with protons), so that the anion exchange membrane can obtain high ion conductivity only when the Ion Exchange Capacity (IEC) is higher, and the IEC is too high to enable the membrane to absorb water and swell strongly, so that the mechanical property of the membrane is greatly reduced, and the use requirement of a battery is difficult to meet. The organic-inorganic composite is a simple and effective method for improving the comprehensive performance of the anion exchange membrane. Hydrotalcite (LDH) is a layered functional material of the general formula [ M ] 1-x 2+ M x 3+ (OH - ) 2 ](A n- ) x/n ·mH 2 O，M 2+ And M 3+ The cations are dispersed in an orderly and uniform manner in the brucite-like layer, the anions are present in the layer to maintain charge conservation, and furthermore, the large number of hydroxyl groups present on the LDH nanoplate surface helps to bind more water molecules, which provides a large number of hydrogen bond networks, which can promote the transport of OH "through the hydrogen bond rapid cleavage/recombination process. Tadanaga et al [ Advanced Materials,2010,22:4401-4404 ] first reported that magnalium hydrotalcite can be used as an electrolyte for alkaline direct ethanol fuel cells to transport OH - And the hydrotalcite prepared by the traditional coprecipitation method and other methods is easy to agglomerate due to strong intermolecular force in the hydrotalcite, so that the ion transmission capacity of the hydrotalcite is greatly reduced. At present, attempts have been made to avoid the agglomeration problem of hydrotalcite during synthesis and incorporation into polymer matrices, zhang et al [ Solid state sciences,2009,11 (9): 1597-1601 ] coating hydrotalcite on nano magnesium ferrite (MgFe) by co-precipitation 2 O 4 ) On the surface of the synthesized sample withThe layered structure has certain magnetism, and on the basis, a core-shell structure model is initially provided. Hydrotalcite grows vertically and uniformly on the surface of a micrometer or nanometer substrate, so that the problem of difficult dispersion of hydrotalcite can be solved, a multi-scale and ordered multi-stage structure hydrotalcite composite material can be constructed, active sites of hydrotalcite composite material are fully exposed, and the anion conduction characteristic of hydrotalcite composite material is exerted. In addition, a cross-linking structure is established for the anion exchange membrane, so that the mobility of a polymer chain in a solvent is poor, and the polymer chain is difficult to swell and dissolve, and therefore, the dimensional stability and the chemical stability of the anion exchange membrane can be ensured under the condition of high ion exchange capacity. However, how to realize the directional arrangement of the multi-stage hydrotalcite in the composite membrane so as to induce the formation of directional ordered ion transmission channels in the membrane, thereby further improving the ion conductivity of the anion exchange membrane is still a difficult problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane, and the prepared composite cross-linked anion exchange membrane has excellent chemical stability (taking the conductivity obtained after the membrane is soaked in a 1mol/LKOH aqueous solution at 60 ℃ for 300 hours as an evaluation index) and mechanical property when the ion conductivity is higher (normal temperature and 80 ℃).
A method for preparing a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane, the method comprising the steps of:
(1) Preparing hydrotalcite coated ferroferric oxide nano particles: transferring glycol solution of sodium acetate trihydrate and ferric trichloride hexahydrate into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 6-12h at 150-220 ℃, cooling the reaction kettle to room temperature, separating out magnetic mud by using a magnet, cleaning the magnetic mud by using deionized water and absolute ethyl alcohol, drying and grinding to obtain nano ferroferric oxide particles; the particle size of the ferroferric oxide nano particles is below 100 nm; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water in a volume ratio of 1:1-1:5 by ultrasonic to form a dispersion liquid with a concentration of 0.1wt.% to 0.5wt.%, firstly dripping a mixed alkali solution into the dispersion liquid until the pH value of the dispersion liquid is 10-11, then dripping the mixed alkali solution and a magnesium salt-aluminum salt mixed solution together for one drop of solution with a dripping speed of three seconds, maintaining the pH value of the solution at 10-11 during dripping, reacting for 12-36 hours at 30-60 ℃ after dripping, cooling, magnetically separating out a magnetic insoluble substance, cleaning the magnetic insoluble substance with deionized water and absolute ethyl alcohol, and drying and grinding to obtain hydrotalcite coated nano ferroferric oxide particles;
further, step (1) contains CH 3 COO - 、Fe 3+ Fe in glycol solution of (C) 3+ The molar concentration of Fe is 0.003-0.007 mol/L 3+ And CH (CH) 3 COO - The molar ratio of (2) is 1:3-1:8; the solvent in the mixed alkali solution and the solvent in the magnesium salt-aluminum salt mixed solution are the same as the solvent in the ferroferric oxide dispersion liquid, and the mixed solvent of methanol and water is the volume ratio of 1:1-1:5; naOH and Na 2 CO 3 Dissolving in mixed solvent to form mixed alkali solution, OH - The molar concentration is 0.2 to 0.3mol/L, OH - With CO 3 2- The molar ratio of (2) is 1:1-1:4; mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O is dissolved in the mixed solvent to form magnesium salt-aluminum salt mixed solution, wherein Mg 2+ The molar concentration of Al is 0.1-0.3 mol/L 3+ With Mg 2+ The molar ratio of Fe is 1:1-1:3 3 O 4 With Mg 2 + In a molar ratio of 1:6, mg 2+ With OH - The molar ratio of (2) is 1:4.
(2) Dispersing the hydrotalcite-coated nano ferroferric oxide particles obtained in the step (1) in a solvent to prepare hydrotalcite-coated ferroferric oxide dispersion liquid with the concentration of 1g/10 mL-1 g/25 mL;
further, the solvent is selected from any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide.
(3) Dissolving quaternized polyphenylene ether in a solvent to form a quaternized polyphenylene ether solution having a concentration of 5 to 30 wt.%;
further, the quaternized polyphenylene ether has a quaternized substitution degree of 20% to 60%, preferably 35% to 55%; more preferably the quaternized polyphenylene ether has a quaternized degree of substitution of 40 to 45%;
further, the solvent is selected from any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide; preferably, the solvent is the same as the solvent used for dispersing hydrotalcite coated ferroferric oxide nano particles in the step (2).
(4) Glutaraldehyde is added into a dimethyl sulfoxide solution of polyvinyl alcohol with the weight percentage of 3.5 to form a polyvinyl alcohol mixed solution, wherein the mass ratio of glutaraldehyde to polyvinyl alcohol is 1:5-1:20; adding the polyvinyl alcohol mixed solution into the quaternized polyphenyl ether solution obtained in the step (3), and uniformly mixing to obtain a quaternized polymer mixed solution, wherein the mass ratio of the polyvinyl alcohol to the quaternized polymer is 1:10-1:100;
(5) Adding the hydrotalcite coated ferroferric oxide dispersion liquid prepared in the step (2) into the quaternized polymer mixed solution prepared in the step (4), wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenyl ether is 1:20-1:100, adjusting the pH value to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain a uniform casting film dispersion liquid;
(6) Pouring the casting film dispersion liquid obtained in the step (5) on a glass plate uniformly, applying a magnetic field with the magnetic field strength of 0.1-0.5T perpendicular to a substrate to the glass plate, naturally drying the glass plate at room temperature for 6-12h, removing the magnetic field, placing the glass plate in an oven at 80 ℃ for continuously drying for 6-12h, cooling to room temperature, removing the film, and performing anion exchange through KOH solution to obtain the magnetic field induced organic-inorganic composite cross-linked anion exchange film.
Further, in the step (6), the anion exchange step is: the membrane is soaked in 1mol/L KOH solution for 1-24h for anion exchange.
The organic-inorganic composite cross-linked anion exchange membrane prepared by the preparation method is provided.
The organic-inorganic composite cross-linked anion exchange membrane prepared by the preparation method is applied to the preparation of alkaline polyelectrolyte fuel cells.
Compared with the prior art, the technical scheme of the invention has the following advantages and beneficial technical effects:
1. compared with hydrotalcite which is easy to agglomerate and is prepared by a stripping/self-assembly method and the like, the method takes nano ferroferric oxide as a hydrotalcite growth substrate (shown in figure 1), and ensures that hydrotalcite grows on the surface of nano ferroferric oxide particles in a vertically staggered orientation by controlling the reaction time and the salt solution concentration to form a honeycomb shape (shown in figure 2), so that hydrotalcite with high specific surface area and high active site is obtained, and the stacking and agglomeration of hydrotalcite are effectively prevented.
2. Compared with the conventional organic-inorganic composite mode, the invention spreads the casting film liquid on the glass substrate and then places the glass substrate in a magnetic field for magnetic field induction, so that the inorganic magnetic particles are arranged in a directional and regular way, on one hand, the agglomeration problem can be greatly reduced, on the other hand, the inorganic particles can also form ion channels with longer range order, and the ion conductivity is further improved.
3. Compared with the general quaternized polyphenyl ether direct film forming, the invention blends the quaternized polyphenyl ether and a small amount of polyvinyl alcohol mixed solution to form a film, the long alkyl chain structure of the polyvinyl alcohol has good toughness, and a large amount of hydroxyl groups in the structure can provide crosslinking sites with glutaraldehyde on one hand, so that the mechanical performance (strength and toughness) and chemical stability of a composite system are enhanced, and more hydroxyl transfer channels can be constructed for the composite crosslinking anion exchange membrane.
In conclusion, the organic-inorganic composite cross-linked anion exchange membrane containing the magnetic field induction of the multi-stage structure prepared by the invention is expected to have wide application prospect in the field of anion exchange membrane fuel cells.
Drawings
FIG. 1 is a scanning electron microscope image of the morphology of the nano ferroferric oxide in example 1.
Fig. 2 is a morphology transmission electron microscope image of the hydrotalcite-coated nano ferroferric oxide prepared in example 1.
Fig. 3 is an XRD pattern of the hydrotalcite-coated nano-ferroferric oxide prepared in example 1.
FIG. 4 is a sectional scanning electron microscope image of the organic-inorganic composite crosslinked basic anion-exchange membrane prepared in example 1.
Detailed Description
The technical solution of the present invention will be further described with reference to specific examples and drawings, but the scope of the present invention is not limited to these examples.
In the following examples, "room temperature" refers to the laboratory ambient temperature without heating or cooling equipment, specifically: 20-25 ℃.
Example 1 a method for preparing a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane comprises the following steps:
(1) Dissolving sodium acetate trihydrate and ferric trichloride hexahydrate in ethylene glycol to form a mixture containing CH 3 COO - 、Fe 3+ Transferring the salt solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 8 hours at 200 ℃, separating out magnetic mud by using a magnet after the reaction kettle is cooled to room temperature, cleaning the magnetic mud by using deionized water and absolute ethyl alcohol, drying and grinding to obtain nano ferroferric oxide particles, wherein a scanning electron microscope image is shown in figure 1; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water in a volume ratio of 1:1 by ultrasonic to form mixed dispersion liquid with a mass percent concentration of 0.3%, and mixing NaOH and Na 2 CO 3 Dissolving in methanol water solution (volume ratio of methanol to water is 1:1) to obtain a solution containing OH - With CO 3 2- Mixing the alkali solution, adding Mg (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O is dissolved in aqueous methanol solution (volume ratio of methanol to water is 1:1) to form Mg-containing solution 2+ And Al 3+ Is used as a salt solution. First to Fe 3 O 4 Dropwise adding a mixed alkali solution into the particle dispersion until the pH of the dispersion is 10-11, simultaneously dropwise adding the mixed alkali solution and the magnesium salt-aluminum salt mixed solution at the same time, keeping the pH of the solution at 10-11 during the dropwise adding period, reacting for 24 hours at 30 ℃, magnetically separating out magnetic insoluble substances after the reaction is finished, cleaning the magnetic insoluble substances with deionized water and absolute ethyl alcohol, drying and grinding to obtain hydrotalcite coated nano-particlesFerroferric oxide particles, denoted as Fe 3 O 4 @ldh, the transmission electron microscopy image of which is shown in fig. 2, and the XRD image of which is shown in fig. 3;
fe in the mixed glycol solution 3+ Is 0.005mol/L, fe 3+ And CH (CH) 3 COO - The molar ratio of (2) is 1:5. The solvent used for the mixed alkali solution and the mixed solution of magnesium salt and aluminum salt is the same as the ferroferric oxide dispersion liquid, and OH in the mixed alkali solution - Molar concentration of 0.3mol/L, OH - With CO 3 2- The molar ratio of (2) is 1:3. Mg in magnesium salt-aluminum salt mixed solution 2+ Is 0.1mol/L, al 3+ With Mg 2+ Is 1:2, fe 3 O 4 With Mg 2+ In a molar ratio of 1:6, mg 2+ With OH - The molar ratio of (2) is 1:4.
(2) Fe obtained in the step (1) 3 O 4 Dispersing the @ LDH in N-methylpyrrolidone to give a dispersion having a concentration of 1g/20 mL.
(3) Quaternized polyphenylene ether (raw material polyphenylene ether is purchased from Synthctical materials Co., ltd., brand LXR045, molecular weight M) W =40000. The preparation process of the quaternized polyphenyl ether comprises the following steps: 10g of dried PPO and 100mL of chlorobenzene are added into a 250mL three-neck flask, nitrogen is introduced, magnetic stirring is carried out at 80 ℃ until the PPO is completely dissolved, 12g N-bromosuccinimide is added as a bromination reagent after cooling to room temperature, 0.8g of dibenzoyl peroxide is taken as an initiator, and condensation reflux reaction is carried out at 80 ℃ for 3 hours under the condition of introducing nitrogen. Cooling to room temperature, precipitating with anhydrous methanol, filtering, washing, drying to obtain brominated polyphenylene oxide, dissolving the obtained brominated polyphenylene oxide in 100 mLN-methylpyrrolidone, adding 1.96g of 1, 2-dimethyl imidazole as quaternizing agent, reacting at 60 ℃ for 24 hours at room temperature, dripping the mixed solution into acetone, filtering to obtain insoluble substances, drying to obtain quaternized polyphenylene oxide, and measuring Br of the quaternized polyphenylene oxide by nuclear magnetic resonance spectroscopy - The content further determines that the quaternized substitution degree is 41 percent) is dissolved in N-methyl pyrrolidone to obtain a quaternized polyphenyl ether solution with the mass percent concentration of 9 percent;
(4) 20. Mu.L of 25wt.% glutaraldehyde in water was added to 1.25mL of a 3.5% strength by mass polyethyleneAlcohols (raw materials are purchased from national pharmaceutical group chemical reagent Co., ltd., average polymerization degree 1750+ -50, pH 5-7 (50 g/L, H) 2 O,25 ℃), melting point 160-240 ℃, density ρ (20 ℃) =0.4-0.6 g/mL, flash point>113 ℃ in dimethyl sulfoxide solution to form a polyvinyl alcohol mixed solution, then adding the polyvinyl alcohol mixed solution into the quaternized polyphenyl ether solution obtained in the step (3), and uniformly mixing to obtain a quaternized polymer mixed solution, wherein the mass ratio of the polyvinyl alcohol to the quaternized polyphenyl ether is 1:20, a step of; and then Fe prepared in the step (2) 3 O 4 Adding the @ LDH dispersion liquid into the mixed solution of the quaternized polymer, adjusting the pH value to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain uniform casting film dispersion liquid, wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenyl ether is 1:100;
(5) Pouring the casting film dispersion liquid obtained in the step (4) on a glass plate uniformly, applying a magnetic field with the magnetic field strength of 0.4T perpendicular to a substrate on the glass plate, naturally drying the glass plate for 6 hours at room temperature, removing the magnetic field, putting the glass plate into an oven at 80 ℃ for continuous drying for 8 hours, cooling the glass plate to room temperature, uncovering the film, finally soaking the film in 1mol/LKOH solution for full anion exchange (24 hours) to obtain the organic-inorganic composite crosslinked anion exchange film induced by the magnetic field, which is simply referred to as an organic-inorganic composite crosslinked basic anion exchange film (film 1), and a section scanning electron microscope image of the organic-inorganic composite crosslinked basic anion exchange film is shown in the figure 4.
For comparison, 1g of quaternized polyphenylene ether was dissolved in N-methylpyrrolidone to obtain a quaternized polyphenylene ether solution having a mass% concentration of 9%, and Fe prepared in the step (2) 3 O 4 Adding the @ LDH dispersion liquid into a quaternized polyphenyl ether solution, adjusting the pH to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain a uniform casting film dispersion liquid, wherein: the added hydrotalcite coated ferroferric oxide and quaternized polyphenyl ether have the mass ratio of 1:100, then casting film dispersion liquid is uniformly poured on a glass plate, a magnetic field with the magnetic field strength of 0.4T vertical to a substrate is applied to the casting film dispersion liquid, the magnetic field is naturally dried for 6 hours at room temperature, then the magnetic field is removed, the drying is carried out in an oven at 80 ℃ for 8 hours, the film is uncovered after cooling to the room temperature, and finally the film is soaked in 1mol/LKOH solution for full anion exchange (24 hours) to obtain the organic matter induced by the magnetic fieldAn inorganic composite anion-exchange membrane, abbreviated as organic-inorganic composite basic anion-exchange membrane (membrane 1-1).
For comparison, 1g of quaternized polyphenylene ether was dissolved in N-methylpyrrolidone to obtain a quaternized polyphenylene ether solution having a mass percent concentration of 9%, and then 20 μl of a 25wt.% glutaraldehyde aqueous solution was added to 1.25mL of a polyvinyl alcohol dimethyl sulfoxide solution having a mass percent concentration of 3.5% to form a polyvinyl alcohol mixed solution, and then the polyvinyl alcohol mixed solution was added to the quaternized polyphenylene ether solution, and the mixture was uniformly mixed to obtain a quaternized polymer mixed solution, wherein the mass ratio of the polyvinyl alcohol to the quaternized polymer was 1:20, a step of; the pH value is regulated to 4 by hydrochloric acid and the mixture is fully stirred and mixed to obtain uniform casting film dispersion liquid, then the casting film dispersion liquid is uniformly poured on a glass plate, the room temperature is naturally dried for 6 hours, then a magnetic field is removed, the casting film dispersion liquid is placed in an oven at 80 ℃ for continuous drying for 8 hours, the film is uncovered after cooling to the room temperature, and finally the film is soaked in 1mol/L KOH solution for full anion exchange (24 hours), so as to obtain a blended cross-linked anion exchange film (film 1-2).
The results of the performance test of the organic-inorganic composite crosslinked basic anion-exchange membrane (membrane 1), the organic-inorganic composite basic anion-exchange membrane (membrane 1-1), and the crosslinked basic anion-exchange membrane (membrane 1-2) prepared in example 1 are shown in table 1:
TABLE 1
From the results shown in table 1, the ionic conductivity of the organic-inorganic composite crosslinked basic anion-exchange membrane (membrane 1) prepared in example 1 is improved by 121% compared with that of the crosslinked basic anion-exchange membrane (membrane 1-2), and the elongation at break of the composite membrane is 7 times that of the organic-inorganic composite basic anion-exchange membrane (membrane 1-1), so that the synergistic enhancement of inorganic matters (hydrotalcite-coated nano ferroferric oxide) and the blended and crosslinked polyvinyl alcohol is remarkably improved, and the stability in alkaline solution is also greatly improved. While the tensile strength, elongation at break and alkaline stability of the crosslinked alkaline anion exchange membrane (membrane 1-2) are improved compared with those of the organic-inorganic composite alkaline anion exchange membrane (membrane 1-1), the ionic conductivity of the crosslinked alkaline anion exchange membrane is difficult to meet the use requirements of the fuel cell.
As can be seen from the scanning electron microscope image of the nanometer ferroferric oxide morphology in the figure 1, the nanometer ferroferric oxide particles are uniformly distributed in thickness, the particle size is about 100nm, and no obvious coating substance exists on the surface; as can be seen from the morphology transmission electron microscope image of the hydrotalcite coated nano ferroferric oxide in FIG. 2, the multi-scale composite material of the two-dimensional lamellar hydrotalcite coated nano ferroferric oxide is formed, and the diameter of the particles is about 200nm; as can be seen from the XRD pattern of the hydrotalcite coated nano ferroferric oxide in figure 3, characteristic diffraction peaks of the hydrotalcite and the ferroferric oxide appear simultaneously, and the characteristic diffraction peaks are compared with the standard patterns of the ferroferric oxide and the magnesium aluminum hydrotalcite, so that the magnesium aluminum hydrotalcite can be generated in situ by the method; as can be seen from the section scanning electron microscope of the organic-inorganic composite cross-linked alkaline anion exchange membrane in FIG. 4, the composite membrane has a very compact section, and a long-chain structure formed by inorganic nanoparticles can be observed, which indicates that the inorganic nanoparticles not only have better dispersibility in a polymer matrix, but also are directionally arranged (arrow direction in FIG. 4) under the action of a magnetic field, and the compact structure is favorable for improving the mechanical property and ion conductivity of the composite membrane.
Example 2 a method for preparing a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane comprises the following steps:
(1) Dissolving sodium acetate trihydrate and ferric trichloride hexahydrate in ethylene glycol to form a mixture containing CH 3 COO - 、Fe 3 + Transferring the salt solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 150 ℃, after the reaction kettle is cooled to room temperature, separating out magnetic mud by using a magnet, cleaning the magnetic mud by using deionized water and absolute ethyl alcohol, and drying and grinding to obtain nano ferroferric oxide particles; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water in a volume ratio of 1:5 by ultrasonic to form a mixed dispersion liquid with a mass percent concentration of 0.1%, and mixing NaOH and Na 2 CO 3 Dissolving in methanol aqueous solution to form a solution containing OH - With CO 3 2- Mixing the alkali solution, adding Mg (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O is dissolved into aqueous methanol solution to form a solution containing Mg 2+ And Al 3+ Is firstly added to Fe 3 O 4 Dropwise adding a mixed alkali solution into the particle dispersion until the pH of the dispersion is 10-11, then dropwise adding the mixed alkali solution and the magnesium salt-aluminum salt mixed solution together, keeping the pH of the solution at 10-11 during the dropwise adding period for 12 hours at 60 ℃, magnetically separating out magnetic insoluble substances after the reaction is finished, cleaning the magnetic insoluble substances with deionized water and absolute ethyl alcohol, drying and grinding to obtain hydrotalcite coated nano ferroferric oxide (Fe) 3 O 4 @ LDH) particles.
Fe in the mixed glycol solution 3+ Molar concentration of 0.003mol/L, fe 3+ And CH (CH) 3 COO - The mol ratio of (1:8), the solvent used for the mixed alkali solution and the mixed solution of magnesium salt and aluminum salt is the same as the ferroferric oxide dispersion liquid, and OH in the mixed alkali solution - Molar concentration of 0.2mol/L, OH - With CO 3 2- The molar ratio of (2) is 1:4. Mg in magnesium salt-aluminum salt mixed solution 2+ Is 0.1mol/L, al 3+ With Mg 2+ Is 1:3, fe 3 O 4 With Mg 2+ In a molar ratio of 1:6, mg 2+ With OH - The molar ratio of (2) is 1:4.
(2) Fe obtained in the step (1) 3 O 4 The @ LDH was dispersed in N, N-dimethylformamide to give a dispersion having a concentration of 1g/20 mL.
(3) Quaternized polyphenylene ether (raw material polyphenylene ether is purchased from Synthctical materials Co., ltd., brand LXR045, molecular weight M) W =40000. The preparation process of the quaternized polyphenyl ether comprises the following steps: 10g of dried PPO and 100mL of chlorobenzene are added into a 250mL three-neck flask, nitrogen is introduced, magnetic stirring is carried out at 80 ℃ until the PPO is completely dissolved, 12g N-bromosuccinimide is added as a brominating reagent after cooling to room temperature, 0.8g of dibenzoyl peroxide is taken as an initiator, and 8g of the mixture is introduced under the condition of nitrogenCondensing and refluxing at 0 ℃ for 3 hours. Cooling to room temperature, precipitating with anhydrous methanol, filtering, washing, drying to obtain brominated polyphenylene oxide, dissolving the obtained brominated polyphenylene oxide in 100 mLN-methylpyrrolidone, adding 1.96g of 1, 2-dimethyl imidazole as quaternizing agent, reacting at 60 ℃ for 24 hours at room temperature, dripping the mixed solution into acetone, filtering to obtain insoluble substances, drying to obtain quaternized polyphenylene oxide, and measuring Br of the quaternized polyphenylene oxide by nuclear magnetic resonance spectroscopy - The content further determines that the quaternized substitution degree is 41 percent) is dissolved in N, N-dimethylformamide to obtain a quaternized polyphenyl ether solution with the mass percent concentration of 9 percent;
(4) Adding 20 mu L of 25wt.% glutaraldehyde water solution into 0.8mL of polyvinyl alcohol dimethyl sulfoxide solution with the mass percentage concentration of 3.5% to form a polyvinyl alcohol mixed solution, adding the polyvinyl alcohol mixed solution into the quaternized polyphenyl ether solution obtained in the step (3), and uniformly mixing to obtain a quaternized polymer mixed solution, wherein the mass ratio of the polyvinyl alcohol to the quaternized polyphenyl ether is 1:20, a step of; and then Fe prepared in the step (2) 3 O 4 Adding the @ LDH dispersion liquid into the mixed solution of the quaternized polymer, adjusting the pH value to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain uniform casting film dispersion liquid, wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenyl ether is 1:25;
(5) Pouring the casting film dispersion liquid obtained in the step (4) on a glass plate uniformly, applying a magnetic field with the magnetic field strength of 0.2T perpendicular to a substrate to the glass plate, naturally drying the glass plate for 6 hours at room temperature, removing the magnetic field, putting the glass plate into an oven at 80 ℃ for continuous drying for 8 hours, cooling the glass plate to room temperature, uncovering the film, finally soaking the film in 1mol/LKOH solution for full anion exchange (24 hours), and obtaining the organic-inorganic composite cross-linked anion exchange film which is induced by the magnetic field, which is abbreviated as the organic-inorganic composite cross-linked alkaline anion exchange film.
Example 3 a method for preparing a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane comprises the following steps:
(1) Dissolving sodium acetate trihydrate and ferric trichloride hexahydrate in ethylene glycol to form a mixture containing CH 3 COO - 、Fe 3 + Is mixed with salt solution of (2) to form saltTransferring the solution into a hydrothermal reaction kettle, performing hydrothermal reaction for 9 hours at 180 ℃, after the reaction kettle is cooled to room temperature, separating out magnetic mud by using a magnet, cleaning the magnetic mud by using deionized water and absolute ethyl alcohol, drying and grinding to obtain nano ferroferric oxide particles; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water in a volume ratio of 1:2 by ultrasonic to form mixed dispersion liquid with a mass percent concentration of 0.4%, and mixing NaOH and Na 2 CO 3 Dissolving in methanol aqueous solution to form a solution containing OH - With CO 3 2- Mixing the alkali solution, adding Mg (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O is dissolved into aqueous methanol solution to form a solution containing Mg 2+ And Al 3+ Is used as a salt solution. First to Fe 3 O 4 Dropwise adding a mixed alkali solution into the particle dispersion until the pH value of the dispersion is 10-11, then dropwise adding the mixed alkali solution and the magnesium salt-aluminum salt mixed solution together, wherein the dropwise adding speed is three seconds and one drop of solution, maintaining the pH value of the solution at 10-11 during the dropwise adding period, reacting at 45 ℃ for 36 hours, magnetically separating out magnetic insoluble substances after the reaction is finished, cleaning the magnetic insoluble substances with deionized water and absolute ethyl alcohol, and drying and grinding to obtain hydrotalcite coated nano ferroferric oxide particles.
Fe in the mixed glycol solution 3+ The molar concentration of (C) is 0.004mol/L, fe 3+ And CH (CH) 3 COO - The molar ratio of (2) is 1:3. The solvent used for the mixed alkali solution and the mixed solution of magnesium salt and aluminum salt is the same as the ferroferric oxide dispersion liquid, and OH in the mixed alkali solution - Molar concentration of 0.04mol/L, OH - With CO 3 2- The molar ratio of (2) is 1:2. Mg in magnesium salt-aluminum salt mixed solution 2+ Is 0.15mol/L, al 3+ With Mg 2+ Is 1:3, fe 3 O 4 With Mg (NO) 3 ) 2 ·6H 2 O in a molar ratio of 1:6, mg 2+ With OH - The molar ratio of (2) is 1:4.
(2) Fe obtained in the step (1) 3 O 4 The @ LDH was dispersed in N, N-dimethylacetamide to give a dispersion having a concentration of 1g/20 mL.
(3) Quaternary ammoniumPolyphenylene ether (polyphenylene ether raw material is purchased from blue star Nantong star synthetic materials Co., ltd., brand LXR045, molecular weight M) W =40000. The preparation process of the quaternized polyphenyl ether comprises the following steps: 10g of dried PPO and 100mL of chlorobenzene are added into a 250mL three-neck flask, nitrogen is introduced, magnetic stirring is carried out at 80 ℃ until the PPO is completely dissolved, 12g N-bromosuccinimide is added as a bromination reagent after cooling to room temperature, 0.8g of dibenzoyl peroxide is taken as an initiator, and condensation reflux reaction is carried out at 80 ℃ for 3 hours under the condition of introducing nitrogen. Cooling to room temperature, precipitating with anhydrous methanol, filtering, washing, drying to obtain brominated polyphenylene oxide, dissolving the obtained brominated polyphenylene oxide in 100 mLN-methylpyrrolidone, adding 1.96g of 1, 2-dimethyl imidazole as quaternizing agent, reacting at 60 ℃ for 24 hours at room temperature, dripping the mixed solution into acetone, filtering to obtain insoluble substances, drying to obtain quaternized polyphenylene oxide, and measuring Br of the quaternized polyphenylene oxide by nuclear magnetic resonance spectroscopy - The content further determines that the quaternized substitution degree is 41 percent) is dissolved in N, N-dimethylacetamide to obtain a quaternized polyphenyl ether solution with the mass percent concentration of 9 percent;
(4) Adding 20 mu L of 25wt.% glutaraldehyde water solution into 2.5mL of polyvinyl alcohol dimethyl sulfoxide solution with the mass percentage concentration of 3.5% to form a polyvinyl alcohol mixed solution, adding the polyvinyl alcohol mixed solution into the quaternized polyphenyl ether solution obtained in the step (3), and uniformly mixing to obtain a quaternized polymer mixed solution, wherein the mass ratio of the polyvinyl alcohol to the quaternized polyphenyl ether is 1:20, a step of; and then Fe prepared in the step (2) 3 O 4 Adding the @ LDH dispersion liquid into the mixed solution of the quaternized polymer, adjusting the pH value to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain uniform casting film dispersion liquid, wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenyl ether is 1:50;
(5) Pouring the casting film dispersion liquid obtained in the step (4) on a glass plate uniformly, applying a magnetic field with the magnetic field strength of 0.4T perpendicular to a substrate to the casting film dispersion liquid, naturally drying the casting film dispersion liquid for 6 hours at room temperature, then placing the casting film dispersion liquid in an oven at 80 ℃ for continuous drying for 8 hours, cooling the casting film dispersion liquid to room temperature, uncovering the casting film dispersion liquid, and finally immersing the casting film dispersion liquid in a 1mol/LKOH solution for full anion exchange (24 hours) to obtain the organic-inorganic composite cross-linked anion exchange film induced by the magnetic field, which is simply called as the organic-inorganic composite cross-linked alkaline anion exchange film.
Example 4 a method for preparing a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane comprises the following steps:
(1) Dissolving sodium acetate trihydrate and ferric trichloride hexahydrate in ethylene glycol to form a mixture containing CH 3 COO - 、Fe 3 + Transferring the salt solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 200 ℃, after the reaction kettle is cooled to room temperature, separating out magnetic mud by using a magnet, cleaning the magnetic mud by using deionized water and absolute ethyl alcohol, and drying and grinding to obtain nano ferroferric oxide particles; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water in a volume ratio of 3:7 by ultrasonic to form a mixed dispersion liquid with a mass percent concentration of 0.5%, and mixing NaOH and Na 2 CO 3 Dissolving in methanol aqueous solution to form a solution containing OH - With CO 3 2- Mixing the alkali solution, adding Mg (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water to form a solution containing Mg 2+ And Al 3+ Is used as a salt solution. First to Fe 3 O 4 Dropwise adding a mixed alkali solution into the particle dispersion until the pH value of the dispersion is 10-11, then dropwise adding the mixed alkali solution and the magnesium salt-aluminum salt mixed solution together, wherein the dropwise adding speed is three seconds and one drop of solution, maintaining the pH value of the solution at 10-11 during the dropwise adding period, reacting for 18 hours at 50 ℃, magnetically separating out magnetic insoluble substances after the reaction is finished, cleaning the magnetic insoluble substances with deionized water and absolute ethyl alcohol, and drying and grinding to obtain hydrotalcite coated nano ferroferric oxide particles.
Fe in the mixed glycol solution 3+ The molar concentration of Fe is 0.007mol/L 3+ And CH (CH) 3 COO - The molar ratio of (2) was 1:7. The solvent used for the mixed alkali solution and the mixed solution of magnesium salt and aluminum salt is the same as the ferroferric oxide dispersion liquid, and OH in the mixed alkali solution - Molar concentration of 0.04mol/L, OH - With CO 3 2- The molar ratio of (2) is 1:2. Mg in magnesium salt-aluminum salt mixed solution 2+ Is 0.25mol/L, al 3+ With Mg 2+ Is 1:2, fe 3 O 4 With Mg (NO) 3 ) 2 ·6H 2 O in a molar ratio of 1:6, mg 2+ With OH - The molar ratio of (2) is 1:4.
(2) Fe obtained in the step (1) 3 O 4 The @ LDH was dispersed in dimethyl sulfoxide to give a dispersion having a concentration of 1g/20 mL.
(3) Quaternized polyphenylene ether (raw material polyphenylene ether is purchased from Synthctical materials Co., ltd., brand LXR045, molecular weight M) W =40000. The preparation process of the quaternized polyphenyl ether comprises the following steps: 10g of dried PPO and 100mL of chlorobenzene are added into a 250mL three-neck flask, nitrogen is introduced, magnetic stirring is carried out at 80 ℃ until the PPO is completely dissolved, 12g N-bromosuccinimide is added as a bromination reagent after cooling to room temperature, 0.8g of dibenzoyl peroxide is taken as an initiator, and condensation reflux reaction is carried out at 80 ℃ for 3 hours under the condition of introducing nitrogen. Cooling to room temperature, precipitating with anhydrous methanol, filtering, washing, drying to obtain brominated polyphenylene oxide, dissolving the obtained brominated polyphenylene oxide in 100 mLN-methylpyrrolidone, adding 2.61g of 1, 2-dimethyl imidazole as quaternizing agent, reacting at 60 ℃ for 24 hours at room temperature, dripping the mixed solution into acetone, filtering to obtain insoluble substances, drying to obtain quaternized polyphenylene oxide, and measuring Br of the quaternized polyphenylene oxide by nuclear magnetic resonance spectroscopy - The content further determines that the quaternized substitution degree is 55 percent) is dissolved in dimethyl sulfoxide to obtain a quaternized polyphenyl ether solution with the mass percent concentration of 9 percent;
(4) Adding 20 mu L of 25wt.% glutaraldehyde water solution into 1.25mL of polyvinyl alcohol dimethyl sulfoxide solution with the mass percentage concentration of 3.5% to form a polyvinyl alcohol mixed solution, adding the polyvinyl alcohol mixed solution into the quaternized polyphenyl ether solution obtained in the step (3), and uniformly mixing to obtain a quaternized polymer mixed solution, wherein the mass ratio of the polyvinyl alcohol to the quaternized polyphenyl ether is 1:20, a step of; and then Fe prepared in the step (2) 3 O 4 Adding the @ LDH dispersion liquid into the mixed solution of the quaternized polymer, adjusting the pH value to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain uniform casting film dispersion liquid, wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenyl ether is 1:20;
(5) Pouring the casting film dispersion liquid obtained in the step (4) on a glass plate uniformly, applying a magnetic field with the magnetic field strength of 0.4T perpendicular to a substrate to the casting film dispersion liquid, naturally drying the casting film dispersion liquid for 6 hours at room temperature, then placing the casting film dispersion liquid in an oven at 80 ℃ for continuous drying for 8 hours, cooling the casting film dispersion liquid to room temperature, uncovering the casting film dispersion liquid, and finally immersing the casting film dispersion liquid in a 1mol/LKOH solution for full anion exchange (24 hours) to obtain the organic-inorganic composite cross-linked anion exchange film induced by the magnetic field, which is simply called as the organic-inorganic composite cross-linked alkaline anion exchange film.
Table 2 shows various performance index data of the organic-inorganic composite crosslinked basic anion exchange membranes prepared in examples 2 to 4. As can be seen from the data in the table, the ionic conductivity of the composite alkaline anion exchange membrane at 80 ℃ is greater than or equal to 45mS cm -1 After soaking in a KOH aqueous solution of 1mol/L at 60 ℃ for 300 hours, the ionic conductivity of the organic-inorganic composite crosslinking alkaline anion exchange membrane at 80 ℃ is more than or equal to 26mS cm -1 And the tensile strength is maintained at a higher level (more than or equal to 35 MPa). Example 4 when preparing an organic-inorganic composite alkaline anion exchange Membrane, the quaternized substitution degree of the quaternized polymer solution used was as high as 55%, and the ion conductivity of the polyelectrolyte membrane prepared was higher (. Gtoreq.70 mS cm) -1 ) But the tensile strength and the alkaline stability are slightly inferior.
TABLE 2
The film performance test conditions prepared in the above examples are described in detail as follows:
(1) Ion conductivity: the resistance of the film was tested on a frequency response analyzer with a frequency sweep in the range of 1-10 6 The amplitude of the alternating current signal was 50mV at Hz. The cut films (length x width = 2.5cm x 1.5 cm) were tested using a two electrode ac impedance method, and prior to testing, the film samples were placed in room temperature deionized water to saturation. The ionic conductivity σ (S/cm) of the membrane is calculated by the following formula:
wherein L and A are the distance between the two electrodes and the effective cross-sectional area of the film to be measured between the two electrodes, R is the resistance of the film, and the Nyquist diagram obtained by the AC impedance test is obtained.
(2) Tensile strength and elongation at break: the film was cut into rectangular bars 40mm long and 10mm wide and tested on an electronic tensile machine at a stretch rate of 1 mm/min.
(3) Alkaline stability: the cut alkaline film (length multiplied by width=3 cm multiplied by 2 cm) is placed in a 60 ℃ 1mol/LKOH aqueous solution for soaking for 300 hours, then is taken out, and is repeatedly washed by deionized water until the washing liquid is neutral, then the ion conductivity of the composite film at 80 ℃ is measured, and the residual ion conductivity is recorded.
Claims (8)
1. A method for preparing a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane, which is characterized by comprising the following steps:
(1) Preparing hydrotalcite coated ferroferric oxide nano particles: transferring glycol solution of sodium acetate trihydrate and ferric trichloride hexahydrate into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 150-220 ℃ for 6-12h, cooling the reaction kettle to room temperature, separating out magnetic mud by using a magnet, cleaning the magnetic mud by using deionized water and absolute ethyl alcohol, drying and grinding to obtain nano ferroferric oxide particles; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water in a volume ratio of 1:1-1:5 by ultrasonic to form a dispersion liquid with a concentration of 0.1: 0.1 wt-0.5: 0.5 wt%, firstly dripping a mixed alkali solution into the dispersion liquid until the pH value of the dispersion liquid is 10-11, then dripping the mixed alkali solution and a magnesium salt-aluminum salt mixed solution together for three seconds, maintaining the pH value of the solution at 10-11 during dripping, reacting at 30-60 ℃ for 12-36h after dripping, cooling, magnetically separating magnetic insoluble substances, cleaning the magnetic insoluble substances with deionized water and absolute ethyl alcohol, and drying and grinding to obtain hydrotalcite coated nano ferroferric oxide particles;
(2) Dispersing the hydrotalcite-coated nano ferroferric oxide particles obtained in the step (1) in a solvent to prepare hydrotalcite-coated ferroferric oxide dispersion liquid with the concentration of 1g/10 mL-1 g/25 mL;
(3) Dissolving quaternized polyphenyl ether in a solvent to form a quaternized polyphenyl ether solution with the concentration of 5-30 wt%, wherein the quaternized polyphenyl ether has the quaternized substitution degree of 20% -60%;
(4) Glutaraldehyde is added into a dimethyl sulfoxide solution of polyvinyl alcohol with the concentration of 3.5-wt percent to form a polyvinyl alcohol mixed solution, wherein the mass ratio of glutaraldehyde to polyvinyl alcohol is 1:5-1:20; adding the polyvinyl alcohol mixed solution into the quaternized polyphenyl ether solution obtained in the step (3), and uniformly mixing to obtain a quaternized polymer mixed solution, wherein the mass ratio of the polyvinyl alcohol to the quaternized polyphenyl ether is 1:10-1:100;
(5) Adding the hydrotalcite coated ferroferric oxide dispersion liquid prepared in the step (2) into the quaternized polymer mixed solution prepared in the step (4), wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenyl ether is 1:20-1:100, adjusting the pH to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain a uniform casting film dispersion liquid;
(6) And (3) uniformly pouring the casting film dispersion liquid obtained in the step (5) on a glass plate, applying a magnetic field with the magnetic field strength of 0.1-0.5T perpendicular to a substrate, naturally drying for 6-12 hours at room temperature, removing the magnetic field, placing the glass plate in an oven at 80 ℃ for continuously drying for 6-12 hours, cooling to room temperature, removing the film, and performing anion exchange through KOH solution to obtain the magnetic field induced organic-inorganic composite cross-linked anion exchange film.
2. The process of claim 1, wherein step (1) comprises CH 3 COO - 、Fe 3+ Fe in glycol solution of (C) 3+ The molar concentration of Fe is 0.003-0.007 mol/L 3+ And CH (CH) 3 COO - The molar ratio of (2) is 1:3-1:8; the solvent used in the mixed alkali solution and the mixed solution of magnesium salt and aluminum salt is the same as the solvent in the ferroferric oxide dispersion liquid, and the mixed alkali solution contains NaOH and Na 2 CO 3 ，OH - The molar concentration is 0.2-0.3 mol/L, OH - With CO 3 2- The molar ratio of (2) is 1:1-1:4; mg in magnesium salt-aluminum salt mixed solution 2+ The molar concentration of Al is 0.1-0.3 mol/L 3+ With Mg 2+ The molar ratio of (2) is 1:1-1:3, fe 3 O 4 With Mg 2+ The molar ratio of (2) is 1:6, mg 2+ With OH - The molar ratio of (2) is 1:4.
3. The production method according to claim 1 or 2, wherein the solvents in steps (2) and (3) are each independently selected from any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide.
4. A process according to claim 3, wherein the solvents in steps (2) and (3) are the same.
5. The method of claim 1, wherein the quaternized polyphenylene ether has a quaternized substitution degree of 35 to 55%.
6. The method of claim 1, wherein the quaternized polyphenylene ether has a degree of quaternized substitution of 40-45%.
7. The method according to claim 1, wherein in the step (6), the anion exchange step is: the membrane was immersed in 1mol/L KOH solution at 1-24. 24h for anion exchange.
8. Use of the organic-inorganic composite cross-linked anion exchange membrane prepared by the preparation method of any one of claims 1 to 7 in the preparation of alkaline polyelectrolyte fuel cells.
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